Golf balls having foam center containing clay particulate

ABSTRACT

Multi-piece golf balls having a solid core made of a foamed composition and a cover are provided. Preferably, the core is dual-layered having has a foam inner core (center) and surrounding thermoset or thermoplastic outer core layer. Preferably, a polyurethane foam composition containing mineral filler particulate, for example, nanoclay particles, is used to form the foam center. The concentration of clay particulate is preferably in a range of 0.1 to 60% by weight. The surrounding outer core layer may be made from non-foamed or foamed compositions. For example, polybutadiene rubber or highly neutralized olefin acid copolymers may be used in the outer core layer. The core layers have different hardness gradients and specific gravity values.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-assigned U.S. patentapplication Ser. No. 15/600,991 filed on May 22, 2017, which is acontinuation of co-assigned U.S. patent application Ser. No. 14/934,447filed on Nov. 6, 2015, now issued as U.S. Pat. No. 9,656,127 with anissue date of May 23, 2017, which is a continuation of co-assigned U.S.patent application Ser. No. 14/060,863 filed on Oct. 23, 2013, nowissued as U.S. Pat. No. 9,180,346 with an issue date of Nov. 10, 2015,the entire disclosures of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates generally to multi-piece, golf ballshaving a solid core made of a foamed composition. Particularly, thedual-layered core has a foam inner core (center) and surroundingthermoset or thermoplastic outer core layer. Preferably, a polyurethanefoam composition containing mineral filler particulate, for example,nanoclay particles, is used to form the foam center. The core layershave different hardness gradients and specific gravity values. The ballfurther includes a cover of at least one layer.

Brief Review of the Related Art

Both professional and amateur golfer use multi-piece, solid golf ballstoday. Basically, a two-piece solid golf ball includes a solid innercore protected by an outer cover. The inner core is made of a natural orsynthetic rubber such as polybutadiene, styrene butadiene, orpolyisoprene. The cover surrounds the inner core and may be made of avariety of materials including ethylene acid copolymer ionomers,polyamides, polyesters, polyurethanes, and polyureas.

In recent years, three-piece, four-piece, and even five-piece balls havebecome more popular. New manufacturing technologies, lower materialcosts, and desirable ball playing performance properties havecontributed to these multi-piece balls becoming more popular. Many golfballs used today have multi-layered cores comprising an inner core andat least one surrounding outer core layer. For example, the inner coremay be made of a relatively soft and resilient material, while the outercore may be made of a harder and more rigid material. The “dual-core”sub-assembly is encapsulated by a cover of at least one layer to providea final ball assembly. Different materials can be used to manufacturethe core and cover and impart desirable properties to the final ball.

In general, dual-cores comprising an inner core (or center) and asurrounding outer core layer are known in the industry. For example,Sugimoto, U.S. Pat. No. 6,390,935 discloses a three-piece golf ballcomprising a core having a center and outer shell and a cover disposedabout the core. The specific gravity of the outer shell is greater thanthe specific gravity of the center. The center has a JIS-C hardness (X)at the center point thereof and a JIS-C hardness (Y) at a surfacethereof satisfying the equation: (Y−X)≥8. The core structure (center andouter shell) has a JIS-C hardness (Z) at a surface of 80 or greater. Thecover has a Shore D hardness of less than 60.

Endo, U.S. Pat. No. 6,520,872 discloses a three-piece golf ballcomprising a center, an intermediate layer formed over the center, and acover formed over the intermediate layer. The center is preferably madeof high-cis polybutadiene rubber; and the intermediate and cover layersare preferably made of an ionomer resin such as an ethylene acidcopolymer.

Watanabe, U.S. Pat. No. 7,160,208 discloses a three-piece golf ballcomprising a rubber-based inner core; a rubber-based outer core layer;and a polyurethane elastomer-based cover. The inner core layer has aJIS-C hardness of 50 to 85; the outer core layer has a JIS-C hardness of70 to 90; and the cover has a Shore D hardness of 46 to 55. Also, theinner core has a specific gravity of more than 1.0, and the core outerlayer has a specific gravity equal to or greater than that of that ofthe inner core.

The core sub-structure located inside of the golf ball acts as an engineor spring for the ball. Thus, the composition and construction of thecore is a key factor in determining the resiliency and reboundingperformance of the ball. In general, the rebounding performance of theball is determined by calculating its initial velocity after beingstruck by the face of the golf club and its outgoing velocity aftermaking impact with a hard surface. More particularly, the “Coefficientof Restitution” or “COR” of a golf ball refers to the ratio of a ball'srebound velocity to its initial incoming velocity when the ball is firedout of an air cannon into a rigid vertical plate. The COR for a golfball is written as a decimal value between zero and one. A golf ball mayhave different COR values at different initial velocities. The UnitedStates Golf Association (USGA) sets limits on the initial velocity ofthe ball so one objective of golf ball manufacturers is to maximize CORunder such conditions. Balls with a higher rebound velocity have ahigher COR value. Such golf balls rebound faster, retain more totalenergy when struck with a club, and have longer flight distance asopposed to balls with low COR values. These properties are particularlyimportant for long distance shots. For example, balls having highresiliency and COR values tend to travel a far distance when struck by adriver club from a tee.

The durability, spin rate, and feel of the ball also are importantproperties. In general, the durability of the ball refers to theimpact-resistance of the ball. Balls having low durability appear wornand damaged even when such balls are used only for brief time periods.In some instances, the cover may be cracked or torn. The spin raterefers to the ball's rate of rotation after it is hit by a club. Ballshaving a relatively high spin rate are advantageous for short distanceshots made with irons and wedges. Professional and highly skilledamateur golfers can place a back spin more easily on such balls. Thishelps a player better control the ball and improves shot accuracy andplacement. By placing the right amount of spin on the ball, the playercan get the ball to stop precisely on the green or place a fade on theball during approach shots. On the other hand, recreational players whocannot intentionally control the spin of the ball when hitting it with aclub are less likely to use high spin balls. For such players, the ballcan spin sideways more easily and drift far-off the course, especiallyif it is hooked or sliced. Meanwhile, the “feel” of the ball generallyrefers to the sensation that a player experiences when striking the ballwith the club and it is a difficult property to quantify. Most playersprefer balls having a soft feel, because the player experience a morenatural and comfortable sensation when their club face makes contactwith these balls. Balls having a softer feel are particularly desirablewhen making short shots around the green, because the player senses morewith such balls. The feel of the ball primarily depends upon thehardness and compression of the ball.

Manufacturers of golf balls are constantly looking to differentmaterials for improving the playing performance and other properties ofthe ball. For example, Kim et al., U.S. Pat. No. 6,794,447 disclosesgolf balls incorporating nanofiller material in their cores, outer coverlayers, or, intermediate layers. The material includes a polymer such aspolyamide, ionomer, polycarbonate, polyurethane, polystyrene,polyethylene, fluoropolymer, polyamide elastomer, thermoplasticpolyolefin, polyester elastomer, polyester, polyolefin, thermoplasticelastomer, thermoplastic vulcanizate, or epoxy resin. Nano-particles ofinorganic material are dispersed in the polymeric material. Theparticles have a size of one micron (μm) or smaller and particlespreferably consist essentially of clay, such as hydrotalcite,montmorillonite, micafluoride, or octosilicate.

Jordan et al., US Patent Application Publication US 2007/0191526discloses golf balls having a core and cover surrounding the core. Atleast one of the layers is formed from a composition comprisingnanoclays and a fully neutralized ethylene acid copolymer or otherionomer resin. The acid groups in the ionomer resin may be neutralizedby a salt of an organic acid, a cation source, or a suitable base. Thenanoclays are described as being high aspect ratio additives typicallybased on montmorillonite clay. The nanoclays preferably have a 50%average dry particle size of 6 μm or less and a 10% average dry particlesize of 2 μm or less with a preferred aspect ratio of 100 to 150.

Sullivan et al., U.S. Pat. No. 7,261,647 discloses golf balls having acore, vapor barrier layer, and cover. The barrier layer is formed from apolymer comprising a nano-material s such as smectite minerals; carbonnanotubes; fullerenes; single-wall and multi-wall carbon nanotubes;polymer nanofibers; and carbon nanofibrils with an average particle sizeof less than 100 nm. According to Sullivan '647, the nano-materialcreates a tortuous path across the barrier layer to prevent vapor frompenetrating therein. Suitable polymers are described as includingionomeric copolymers and terpolymers, thermoplastic elastomers,polybutadiene rubber, balata, grafted metallocene-catalyzed polymers,polyurethanes, and polyureas.

One drawback with adding mineral fillers, particularly nanometer-sizedmaterials (“nano-materials”), is that such fillers are often difficultto disperse in the composition. The very small size of thenano-particles makes them hard to disperse fully and uniformly. As aresult, agglomerates of nano-particles may form in the polymeric matrix.If a significant amount of agglomerates and aggregates form, they maynegatively affect physical properties of the composition such ascompression strength, flexural modulus, tensile strength, elongation atbreak, and the like.

Thus, it would be desirable to have a composition containingnano-materials that are dispersed effectively throughout thecomposition. The nano-materials should be dispersed fully and uniformlyto form a homogeneous mixture that can be molded easily into a golf ballcore. In addition, the nano-materials should help enhance the physicaland mechanical properties of the core. The resulting ball also shouldhave good resiliency since this allows players to generate higherinitial ball speed and make shots having greater distance. The presentinvention provides new foam core constructions having such properties aswell as other advantageous features and benefits. The invention alsoencompasses golf balls containing the improved core constructions.

SUMMARY OF THE INVENTION

The present invention provides a multi-piece golf ball comprising asolid core having at least two layers and a cover having at least onelayer. In one version, the dual-layered core includes: i) an inner core(center) comprising a foamed composition, wherein the inner core has adiameter in the range of about 0.100 to about 1.100 inches and aspecific gravity (SG and ii) an outer core layer comprising a non-foamedthermoset or thermoplastic material, wherein the outer core layer isdisposed about the inner core and has a thickness in the range of about0.100 to about 0.750 inches and a specific gravity (SG_(outer)).Preferably, the SG_(outer) is greater than the SG_(inner).

Preferably, the inner core comprises a foam polyurethane compositioncomprising mineral filler particulate in an amount of about 0.1 to about9.0% by weight based on the weight of the composition. The polyurethanefoam is prepared from a mixture comprising polyisocyanate, polyol,mineral filler particulate, curing agent compounds, and blowing agent.Aromatic and aliphatic polyisocyanates may be used. The foamedpolyurethane composition may be prepared by using water as a blowingagent. The water is added to the mixture in a sufficient amount to causethe mixture to foam. In one preferred version, the mineral fillerparticulate comprises clay particulate. For example a mixture ofdifferent clay particles, the particles having an average specificgravity in the range of about 1.30 to about 3.00 g/cc may be used.Nanoclay particulate also may be used. The nanoclay particles may havesurfaces chemically-modified with a compound selected from the groupconsisting of ammonium compounds, protonated amines, organic phosphoniumions, and/or aminocarboxylic acid, preferable a quaternary ammoniumcompound.

Thermoset or thermoplastic materials are used to form the outer corelayer in the present invention. Preferably, the thermoset andthermoplastic materials are non-foamed. Thus, the dual-core includes afoam inner core (center) and a surrounding non-foamed thermoset corelayer. The inner core layer may have different thicknesses and specificgravities. For example, the inner core may have a diameter in the rangeof about 0.100 to about 0.900 inches, particularly 0.400 to 0.800inches; and a specific gravity in the range of about 0.25 to about 1.25g/cc, particularly 0.30 to 0.95 g/cc. For example, the outer core layermay have a thickness in the range of about 0.250 to about 0.750 inchesand a specific gravity in the range of about 0.60 to about 2.90 g/cc.

The core layers may have different hardness gradients. For example, eachcore layer may have a positive, zero, or negative hardness gradient. Ina first embodiment, the inner core has a positive hardness gradient; andthe outer core layer has a positive hardness gradient. In a secondembodiment, the inner core has a positive hardness gradient, and theouter core layer has zero or negative hardness gradient. In yet anotherversion, the inner core has a zero or negative hardness gradient; andthe outer core layer has a positive hardness gradient. In anotheralternative version, both the inner and outer core layers have zero ornegative hardness gradients.

In one preferred embodiment of this invention, the core has adjoiningfoam layers. For example, the inner core (center) may comprise a firstfoamed polyurethane composition, and the outer core layer may comprise asecond foamed polyurethane composition. Preferably, the inner core has adiameter in the range of about 0.100 to about 1.100 inches and aspecific gravity (SG_(inner)); and the outer core has a thickness in therange of about 0.100 to about 0.750 inches and a specific gravity(SG_(outer)), wherein SG_(outer) is greater than the SG_(inner). Asdiscussed above, mineral fillers, particularly nanoclay particulate, maybe added to the foamed compositions.

In another embodiment, a multi-piece golf ball comprising a solid corehaving three layers and a cover having at least one layer is made. Thisball may have different constructions. For example, in one version, themulti-layered core includes: i) an inner core (center) comprising afoamed composition, wherein the inner core has a diameter in the rangeof about 0.100 to about 1.100 inches and a specific gravity(SG_(inner)); ii) an intermediate layer comprising a non-foamedthermoset or thermoplastic material, wherein the intermediate layer isdisposed about the inner core and has a thickness in the range of about0.050 to about 0.400 inches and a specific gravity (SG_(intermediate));and iii) an outer core layer comprising a thermoset material, whereinthe outer cover layer is disposed about the intermediate core layer andhas a thickness in the range of about 0.200 to about 0.750 inches and aspecific gravity (SG_(outer)). Preferably, the SG_(inner) is less thanthe SG_(intermediate) and SG_(outer). That is, the SG_(outer) is greaterthan the SG_(inner) and the SG_(intermediate) is greater than theSG_(inner). In another version, the outer core layer is made of athermoplastic composition.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features that are characteristic of the present invention areset forth in the appended claims. However, the preferred embodiments ofthe invention, together with further objects and attendant advantages,are best understood by reference to the following detailed descriptionin connection with the accompanying drawings in which:

FIG. 1 is a perspective view of a spherical inner core made of a foamedcomposition in accordance with the present invention;

FIG. 2 is a perspective view of one embodiment of upper and lower moldcavities used to make the dual-layered cores of the present invention;

FIG. 3 is a cross-sectional view of a three-piece golf ball having adual-layered core made in accordance with the present invention;

FIG. 4 is a cross-sectional view of a four-piece golf ball having adual-layered core made in accordance with the present invention;

FIG. 5 is a graph showing the hardness of a two (2) differentdual-layered core samples (each sample having a foam center andthermoset rubber outer layer) at different points in the respective corestructures per two examples of this invention;

FIG. 6 is a photograph (top-view) showing the foam morphology of apolyurethane foam composition that does not contain clay particulate(Comparative Sample);

FIG. 7 is a photograph (top-view) showing the foam morphology of apolyurethane foam composition containing clay particulate in accordancewith this invention; and

FIG. 8 is a photograph showing a column of a polyurethane foamcomposition containing clay particulate made in accordance with thisinvention (Sample F) versus a column of a polyurethane foam compositionthat does not contain any clay particulate (Sample E).

DETAILED DESCRIPTION OF THE INVENTION

Golf Ball Constructions

Golf balls having various constructions may be made in accordance withthis invention. For example, golf balls having three piece, four-piece,and five-piece constructions with single or multi-layered covermaterials may be made. Representative illustrations of such golf ballconstructions are provided and discussed further below. The term,“layer” as used herein means generally any spherical portion of the golfball. More particularly, in one version, a three-piece golf ballcontaining a dual-layered core and single-layered cover is made. Thedual-core includes an inner core (center) and surrounding outer corelayer. In another version, a four-piece golf ball containing a dual-coreand dual-cover (inner cover and outer cover layers) is made. In yetanother construction, a four-piece or five-piece golf ball containing adual-core; casing layer(s); and cover layer(s) may be made. As usedherein, the term, “casing layer” means a layer of the ball disposedbetween the multi-layered core sub-assembly and cover. The casing layeralso may be referred to as a mantle or intermediate layer. The diameterand thickness of the different layers along with properties such ashardness and compression may vary depending upon the construction anddesired playing performance properties of the golf ball.

Inner Core Composition

In general, foam compositions are made by forming gas bubbles in apolymer mixture using a foaming (blowing) agent. As the bubbles form,the mixture expands and forms a foam composition that can be molded intoan end-use product having either an open or closed cellular structure.Flexible foams generally have an open cell structure, where the cellswalls are incomplete and contain small holes through which liquid andair can permeate. Such flexible foams are used for automobile seats,cushioning, mattresses, and the like. Rigid foams generally have aclosed cell structure, where the cell walls are continuous and complete,and are used for used for automobile panels and parts, buildinginsulation and the like.

In the present invention, the inner core (center) comprises alightweight foam thermoplastic or thermoset polymer composition that mayrange from relatively rigid foam to very flexible foam. Referring toFIG. 1, a foamed inner core (4) having a geometric center (6) and outerskin (8) may be prepared in accordance with this invention.

A wide variety of thermoplastic and thermoset materials may be used informing the foam composition of this invention including, for example,polyurethanes; polyureas; copolymers, blends and hybrids of polyurethaneand polyurea; olefin-based copolymer ionomer resins (for example,Surlyn® ionomer resins and DuPont HPF® 1000 and HPF® 2000, commerciallyavailable from DuPont; Iotek® ionomers, commercially available fromExxonMobil Chemical Company; Amplify® 10 ionomers of ethylene acrylicacid copolymers, commercially available from Dow Chemical Company; andClarix® ionomer resins, commercially available from A. Schulman Inc.);polyethylene, including, for example, low density polyethylene, linearlow density polyethylene, and high density polyethylene; polypropylene;rubber-toughened olefin polymers; acid copolymers, for example,poly(meth)acrylic acid, which do not become part of an ionomericcopolymer; plastomers; flexomers; styrene/butadiene/styrene blockcopolymers; styrene/ethylene-butylene/styrene block copolymers;dynamically vulcanized elastomers; copolymers of ethylene and vinylacetates; copolymers of ethylene and methyl acrylates; polyvinylchloride resins; polyamides, poly(amide-ester) elastomers, and graftcopolymers of ionomer and polyamide including, for example, Pebax®thermoplastic polyether block amides, commercially available from ArkemaInc; cross-linked trans-polyisoprene and blends thereof; polyester-basedthermoplastic elastomers, such as Hytrel®, commercially available fromDuPont or RiteFlex®, commercially available from Ticona EngineeringPolymers; polyurethane-based thermoplastic elastomers, such asElastollan®, commercially available from BASF; synthetic or naturalvulcanized rubber; and combinations thereof. Castable polyurethanes,polyureas, and hybrids of polyurethanes-polyureas are particularlydesirable because these materials can be used to make a golf ball havinggood playing performance properties as discussed further below. By theterm, “hybrids of polyurethane and polyurea,” it is meant to includecopolymers and blends thereof.

Basically, polyurethane compositions contain urethane linkages formed bythe reaction of a multi-functional isocyanate containing two or more NCOgroups with a polyol having two or more hydroxyl groups (OH—OH)sometimes in the presence of a catalyst and other additives. Generally,polyurethanes can be produced in a single-step reaction (one-shot) or ina two-step reaction via a prepolymer or quasi-prepolymer. In theone-shot method, all of the components are combined at once, that is,all of the raw ingredients are added to a reaction vessel, and thereaction is allowed to take place. In the prepolymer method, an excessof polyisocyanate is first reacted with some amount of a polyol to formthe prepolymer which contains reactive NCO groups. This prepolymer isthen reacted again with a chain extender or curing agent polyol to formthe final polyurethane. Polyurea compositions, which are distinct fromthe above-described polyurethanes, also can be formed. In general,polyurea compositions contain urea linkages formed by reacting anisocyanate group (—N═C═O) with an amine group (NH or NH₂). Polyureas canbe produced in similar fashion to polyurethanes by either a one shot orprepolymer method. In forming a polyurea polymer, the polyol would besubstituted with a suitable polyamine. Hybrid compositions containingurethane and urea linkages also may be produced. For example, whenpolyurethane prepolymer is reacted with amine-terminated curing agentsduring the chain-extending step, any excess isocyanate groups in theprepolymer will react with the amine groups in the curing agent. Theresulting polyurethane-urea composition contains urethane and urealinkages and may be referred to as a hybrid. In another example, ahybrid composition may be produced when a polyurea prepolymer is reactedwith a hydroxyl-terminated curing agent. A wide variety of isocyanates,polyols, polyamines, and curing agents can be used to form thepolyurethane and polyurea compositions as discussed further below.

To prepare the foamed polyurethane, polyurea, or other polymercomposition, a foaming agent is introduced into the polymer formulation.In general, there are two types of foaming agents: physical foamingagents and chemical foaming agents.

Physical Foaming Agents.

These foaming agents typically are gasses that are introduced under highpressure directly into the polymer composition. Chlorofluorocarbons(CFCs) and partially halogenated chlorofluorocarbons are effective, butthese compounds are banned in many countries because of theirenvironmental side effects. Alternatively, aliphatic and cyclichydrocarbon gasses such as isobutene and pentane may be used. Inertgasses, such as carbon dioxide and nitrogen, also are suitable. Withphysical foaming agents, the isocyanate and polyol compounds react toform polyurethane linkages and the reaction generates heat. Foam cellsare generated and as the foaming agent vaporizes, the gas becomestrapped in the cells of the foam.

Chemical Foaming Agents.

These foaming agents typically are in the form of powder, pellets, orliquids and they are added to the composition, where they decompose orreact during heating and generate gaseous by-products (for example,nitrogen or carbon dioxide). The gas is dispersed and trapped throughoutthe composition and foams it. For example, water may be used as thefoaming agent. Air bubbles are introduced into the mixture of theisocyanate and polyol compounds and water by high-speed mixingequipment. As discussed in more detail further below, the isocyanatesreact with the water to generate carbon dioxide which fills and expandsthe cells created during the mixing process.

Preferably, a chemical foaming agent is used to prepare the foamcompositions of this invention. Chemical blowing agents may beinorganic, such as ammonium carbonate and carbonates of alkalai metals,or may be organic, such as azo and diazo compounds, such asnitrogen-based azo compounds. Suitable azo compounds include, but arenot limited to, 2,2′-azobis(2-cyanobutane),2,2′-azobis(methylbutyronitrile), azodicarbonamide, p,p′-oxybis(benzenesulfonyl hydrazide), p-toluene sulfonyl semicarbazide, p-toluenesulfonyl hydrazide. Other foaming agents include any of the Celogens®sold by Crompton Chemical Corporation, and nitroso compounds,sulfonylhydrazides, azides of organic acids and their analogs,triazines, tri- and tetrazole derivatives, sulfonyl semicarbazides, ureaderivatives, guanidine derivatives, and esters such as alkoxyboroxines.Also, foaming agents that liberate gasses as a result of chemicalinteraction between components such as mixtures of acids and metals,mixtures of organic acids and inorganic carbonates, mixtures of nitrilesand ammonium salts, and the hydrolytic decomposition of urea may beused. Water is a preferred foaming agent. When added to the polyurethaneformulation, water will react with the isocyanate groups and formcarbamic acid intermediates. The carbamic acids readily decarboxylate toform an amine and carbon dioxide. The newly formed amine can thenfurther react with other isocyanate groups to form urea linkages and thecarbon dioxide forms the bubbles to produce the foam.

During the decomposition reaction of certain chemical foaming agents,more heat and energy is released than is needed for the reaction. Oncethe decomposition has started, it continues for a relatively long timeperiod. If these foaming agents are used, longer cooling periods aregenerally required. Hydrazide and azo-based compounds often are used asexothermic foaming agents. On the other hand, endothermic foaming agentsneed energy for decomposition. Thus, the release of the gasses quicklystops after the supply of heat to the composition has been terminated.If the composition is produced using these foaming agents, shortercooling periods are needed. Bicarbonate and citric acid-based foamingagents can be used as exothermic foaming agents.

Other suitable foaming agents include expandable gas-containingmicrospheres. Exemplary microspheres consist of an acrylonitrile polymershell encapsulating a volatile gas, such as isopentane gas. This gas iscontained within the sphere as a blowing agent. In their unexpandedstate, the diameter of these hollow spheres range from 10 to 17 μm andhave a true density of 1000 to 1300 kg/m³. When heated, the gas insidethe shell increases its pressure and the thermoplastic shell softens,resulting in a dramatic increase of the volume of the microspheres.Fully expanded, the volume of the microspheres will increase more than40 times (typical diameter values would be an increase from 10 to 40μm), resulting in a true density below 30 kg/m³ (0.25 lbs/gallon).Typical expansion temperatures range from 80-190° C. (176-374° F.). Suchexpandable microspheres are commercially available as Expancel® fromExpancel of Sweden or Akzo Nobel.

As an alternative to chemical and physical foaming agents or in additionto such foaming agents, as described above, other types of fillers thatlower the specific gravity of the composition can be used in accordancewith this invention. For example, polymeric, ceramic, and glass unfilledmicrospheres having a density of 0.1 to 1.0 g/cc and an average particlesize of 10 to 250 microns can be used to help lower specific gravity ofthe composition and achieve the desired density and physical properties.

Additionally, BASF polyurethane materials sold under the trade nameCellasto® and Elastocell®, microcellular polyurethanes, Elastopor® Hthat is a closed-cell polyurethane rigid foam, Elastoflex® W flexiblefoam systems, Elastoflex®E semiflexible foam systems, Elastofoam®flexible integrally-skinning systems, Elastolit®D/K/R integral rigidfoams, Elastopan®S, Elastollan® thermoplastic polyurethane elastomers(TPUs), and the like may be used in accordance with the presentinvention. Bayer also produces a variety of materials sold as Texin®TPUs, Baytec® and Vulkollan® elastomers, Baymer® rigid foams, Baydur®integral skinning foams, Bayfit® flexible foams available as castable,RIM grades, sprayable, and the like that may be used. Additional foammaterials that may be used herein include polyisocyanurate foams and avariety of “thermoplastic” foams, which may be cross-linked to varyingextents using free-radical (for example, peroxide) or radiationcross-linking (for example, UV, IR, Gamma, EB irradiation). Also, foamsmay be prepared from polybutadiene, polystyrene, polyolefin (includingmetallocene and other single site catalyzed polymers), ethylene vinylacetate (EVA), acrylate copolymers, such as EMA, EBA, Nucrel®-type acidco and terpolymers, ethylene propylene rubber (such as EPR, EPDM, andany ethylene copolymers), styrene-butadiene, and SEBS (any Kraton-type),PVC, PVDC, CPE (chlorinated polyethylene). Epoxy foams,urea-formaldehyde foams, latex foams and sponge, silicone foams,fluoropolymer foams and syntactic foams (hollow sphere filled) also maybe used.

In addition to the polymer and foaming agent, the foam composition alsomay include other ingredients such as, for example, cross-linkingagents, chain extenders, surfactants, dyes and pigments, coloringagents, fluorescent agents, adsorbents, stabilizers, softening agents,impact modifiers, antioxidants, antiozonants, and the like. Theformulations used to prepare the polyurethane foam compositions of thisinvention preferably contain a polyol, polyisocyanate, water, an amineor hydroxyl curing agent, surfactant, and a catalyst as describedfurther below.

In one preferred version, the foam composition contains mineral fillerparticulate. Suitable mineral filler particulates include compounds suchas zinc oxide, limestone, silica, mica, barytes, lithopone, zincsulfide, talc, calcium carbonate, magnesium carbonate, clays, powderedmetals and alloys such as bismuth, brass, bronze, cobalt, copper, iron,nickel, tungsten, aluminum, tin, precipitated hydrated silica, fumedsilica, mica, calcium metasilicate, barium sulfate, zinc sulfide,lithopone, silicates, silicon carbide, diatomaceous earth, carbonatessuch as calcium or magnesium or barium carbonate, sulfates such ascalcium or magnesium or barium sulfate. As discussed further below, themineral fillers tend to help decrease the size of the foam cells andincrease cell density. The fillers also tend to help improve thephysical properties of the foam such as hardness, compression set, andtensile strength.

The preferred mineral fillers include clays, organoclays,organically-modified clays, and nanoclays. By the term, “clay” it ismeant many combinations of minerals with traces of metal oxides andorganic matter. Geologic clay deposits are formed from the decompositionand weathering of rock and are mostly composed of phyllosilicateminerals containing variable amounts of water trapped in the mineralstructure. These include the layered silicates; metal oxides;hydroxides; and oxy-oxides. Silicate clays are commonly grouped intoeither kaolinite, montmorillonite-smectite, illite and chlorite, orvermiculite families. Sesquioxide clays (metal oxides and hydrousoxides), allophanes and imogolite, carbonate and sulfate minerals, areall examples of mineral filler particulates. Kaolin clays include waterwashed clays, surface-treated water-washed clays, delaminated clays andcalcined clays. The preferred layered materials include smectite clayminerals such as montmorillonite, sodium montmorillonite; magnesiummontmorillonite; and/or calcium montmorillonite nontronite, beidellite,volkonskoite, hectorite, saponite, sauconite, sobockite, stevensite, andsvinfordite. Clay minerals are generally hydrated aluminum silicateminerals and comprise tetrahedral silicate sheets and octahedralhydroxide sheets. In general, the clays can be classified as 1:1 or 2:1layered minerals. A 1:1 clay would contain one tetrahedral sheet and oneoctahedral sheet. Examples of such 1:1 clays include kaolinite andserpentine. A 2:1 layered clay contains an octahedral sheet sandwichedbetween two tetrahedral sheets, and examples are talc, vermiculite, andmontmorillonite.

Such clay and other mineral fillers are described in the patentliteratures, for example, Gadberry et al., U.S. Pat. No. 5,663,111;Dennis, U.S. Pat. No. 5,739,087; Gonzales et al., U.S. Pat. No.5,780,376; Farrow et al., U.S. Pat. Nos. 6,036,765 and 6,534,570 and6,635,108; Powell et al., U.S. Pat. No. 6,787,592; and Bauer et al.,U.S. Pat. No. 6,890,502, the disclosures of which are herebyincorporated by reference. The surfaces of the mineral fillerparticulate may be chemically-modified to make the particulatecompatible with a polymer matrix. This surface-treatment helps improvethe blending and dispersion of the particulate in the polymer matrix asdescribed further below. Suitable mineral filler particulate that may beused in the foam formulations include, but is not limited to, Garamite®mixed mineral thixotropes, commercially available from Southern ClayProducts, Inc. It is believed the Garamite® mixed mineral thixotropes isa clay material comprising a mixture of different clay materials,particularly saponite clay materials which belong to the smectite familyas described above and sepiolite clay, which is a hydrous magnesiumsilicate clay. Unlike many clays which are layered phyliosilicates asdescribed above, sepiolite clay miner comprises tiny elongated,needle-like particles. The tiny elongated particles of sepiolite have anaverage length of 1 μm to 2 μm, a width of 0.01 μm; and contain openchannels with dimensions of 3.6 Å×10.6 Å running along the axis of theparticle.

The mineral filler included in the foam-forming mixture of the presentinvention is generally included in an amount of about 0.1 to about 60%by weight, preferably about 0.1% to about 9% by weight, and morepreferably about 1% to about 5% by weight, based on total weight of thefoam composition. In some embodiments, the composition may contain asubstantial amount of filler, for example, greater than about 25% andeven greater than about 50% by weight. More particularly, the mineralfiller may be present in an amount of about 50 to about 60% by weight.In general, the mineral filler has an average particle size in the rangeof about 1 to about 25 microns, preferably about 1 to about 5 microns;however, particles having sub-micron particle sizes may be used inaccordance with this invention as described further below. For example,nanometer-sized particles having a particle size of 1 to 100 nanometers(0.001 to 0.1 microns) may be used. The mineral filler particles,particularly the nanoclay particles, preferably have an average specificgravity within the range of about 1.3 to about 3.0 g/cc, more preferablyin the range of about 1.4 to about 2.8 g/cc, particularly about 1.5 toabout 2.0 g/cc.

It is generally known to use mineral fillers as reinforcing agents inpolymer resins. However, polyurethane foam compositions are uniquematerials. As discussed above, the foam-forming mixture contains variousreactants including polyisocyanates, polyols, curing agents,surfactants, and catalysts. Special care should be taken when addingmineral fillers to a polyurethane foam-forming mixture, because thefillers can significantly affect the foam cells being generated, forexample, cell growth and cell morphology. The fillers also can affectphysical properties of the foam. As discussed above, various mineralparticles may be used in accordance with this invention. However, in apreferred version, nanoclay particles are included in the foamcomposition.

In general, nanoclays refer to clays from the smectite family having asheet-like or platey structure with at least one dimension in thenanometer range. The smectite family includes, for example,montmorillonite, hectorite, saponite, and beidellite clays. For example,montmorillonite-based nanoclays are 2-to-1 layered minerals from thesmectite clay family. Each layer has two silica tetradedral sheetscontaining an octahedral sheet of aluminum hydroxide between them. Thediscrete montmorillonite particles generally have a platelet shape and asheet-like structure with dimensions in two directions that far exceedthe particle's thickness. Particularly, the particles have a thicknessof just one nanometer, but their surface dimensions are generally 300 to600 nanometers resulting in particles having a very high aspect ratio.For example, the aspect ratio (length over width) can fall within therange of 200 to 1000 with many particles in the range of 200 to 400.Because of their high aspect ratios and high surface areas, the nanolcayparticles clay can help impart various physical and chemical propertiesto the foam composition. In the clay's natural form, the clay particlesare attracted to each other by naturally-occurring ions on theirsurfaces. Such non-modified clay particles tend to be organophobic andform agglomerates when they are introduced into a polymer matrix.

Thus, the surfaces of the nanoclay particles are normallychemically-modified to make them compatible with a polymer matrix.During chemical surface-treatment, the naturally-occurring cations foundon the particles' surfaces are replaced with organocations. Differentsurface-modifying chemistries may be used. Compounds suitable formodifying the surfaces of the clay particles are known in the nanoclayindustry. In particular, quaternary onium compounds may be used,preferably quaternary ammonium compounds. Suitable compounds alsoencompass protonated amines, organic phosphonium ions, and/oraminocarboxylic acids. For example, the surfaces may be modified withprimary amines, methacryloyloxyethylhexadecyl-dimethyl ammoniums, ormethyl tallow bis-2-hydroxyethyl quaternary ammonia salts. Thistreatment makes the particles organophillic—the particles become moreattracted to and can be dispersed fully in the polymer matrix.

As the organic chemical enters the clay structure and bonds to thesurfaces of the clay particles, a clay-chemical complex is formed. Thisstep is commonly referred to as intercalation. The spacing between theparticles (platelets) of the clay is increased during the intercalationstep, but there is still a defined spatial relationship between theparticles. This “gallery space” (inter-layer spacing) may vary dependingupon the type of molecules and chemical surface-treatment applied. Inthe next step, the clay particles are exfoliated. That is, the clayparticles are completely separated from each other—this separationenables the particles to become fully dispersed in the polymer matrix.

Suitable nanoclay particulate that may be used in the foam formulationsinclude, but are not limited to, Cloisite® and Nanofil® commerciallyavailable from Southern Clay Products, Inc.; and Nanomax® and Nanomer®nanoclays, commercially available from Nanocor, Inc. Preferably, thefoam composition contains about 0.1 to about 9.0%, preferably 0.25 toabout 5%, and more preferably about 0.35 to about 1.00% by weight ofnanoclay particles based on total weight of the composition.

As discussed above, polyurethanes can generally be produced in asingle-step reaction (one-shot) or in a two-step reaction via aprepolymer or quasi-prepolymer step. In the one-shot method, all of thecomponents (polyol, polyisocyanate, blowing agents such as water), anamine and/or hydroxyl curing agent, surfactant, and catalyst arecombined at once. Thus, all of the raw ingredients are added to areaction vessel, and the reaction is allowed to take place. In thisone-shot reaction method, the nanoclay particulate or other mineralfiller may be added to the polymeric adduct of the polyol orpolyisocyanate prior to the reaction. Using this procedure, the nanoclayparticles are pre-dispersed in the polyol or polyisocyanate, where theirfunctional groups (for example, isocyanate or hydroxyl groups) may reactwith the chemically-modified surface of the nanoclay particles (forexample, quartenary ammonia salts). Also, as discussed above, when wateris added to the reaction mixture, the water will react with theisocyanate groups and form carbamic acid intermediates, and the carbamicacids decompose to form amines. The quartenary ammonia salts or otherchemically reactive groups on the surface of the nanoclay particles mayreact with these free amine groups. This can change the reaction rate ofthe reactants in the mixture. On the other hand, in the prepolymermethod, an excess of polyisocyanate is first reacted with some amount ofa polyol to form the prepolymer which contains reactive NCO groups. Thisprepolymer is then reacted again with a chain extender (curing agent) toform the polyurethane. Here, the nanoclay particulate is pre-dispersedin the chain extender (curing agent) and then this mixture is reactedwith the prepolymer. In the present invention, it is preferred theprepolymer method be used, wherein a pre-mixture of nanoclay/chainextender is prepared and then mixed and reacted with the prepolymer.Using this prepolymer method, the pre-mixture of nanoclay/chain extenderis homogeneously mixed with the prepolymer composition and the nanoclayparticles are effectively dispersed. The reaction between thechemically-modified nanoclay particle surfaces and functional groups ofthe other ingredients are minimized. The nanoclay particulate isdispersed uniformly in the composition and the tendency of the particlesto stick together and form aggregates is minimized.

Because the nanometer-sized clay particles have a very high aspect ratioand are close in scale to the molecules of the polymer resin, they canclosely interact with the resin and create constrained regions withinthe resin. In turn, the mechanical properties of the foam are improved.The nanoclay particles help improve compressive strength, impactstrength, modulus, and other physical properties of the foams. Thenanoclay particles also help create an effective gas vapor barrier. Forexample, the small and flexible nanoclay particles are dispersedthroughout the polymer matrix and form a tortuous pathway to prevent gasfrom diffusing out of the foam material

While not wishing to be bound by any theory, it is believed that addingthe nanoclay particles to the foam composition helps improve the foamcell structure and morphology due to the interaction of the nanoclay andreactants in the foam mixture. As the nanoclay particles are introducedand dispersed in the foam mixture, they help create a greater number ofsmaller sized foam cells. The generated foam cells are packed togethermore tightly and cell density is increased. Also, the dimensions andgeometry of the foam cells tends to be more uniform. The cell structurein the foam is maintained as the nanoclay particles help prevent gasfrom diffusing out through the cell walls. The resulting foam materialtends to have greater compression strength and modulus. Also, thepolyurethane foam containing the nanoclay particles tends to have fastercream time. That is, the foam rises quickly, particularly there isrelatively short time period from the point of mixing the rawingredients together to the point where the mixture turns cloudy inappearance or changes color and begins to rise from its initial stablestate.

As discussed further below, in one preferred embodiment, the specificgravity (density) of the foam inner core is less than the specificgravity of the outer core. In this embodiment, it is important that asufficient amount of nanoclay particles be added to the composition toimprove cell structure and morphology. However, an excess amount ofnanoclay particles should not be added to increase the specific gravity(density) of the foam inner core to a level such that it would begreater than the specific gravity of the outer core layer. If the ball'smass is concentrated towards the outer surface (for example, outer corelayers), and the outer core layer has a higher specific gravity than theinner core, the ball has a relatively high Moment of Inertia (MOI). Insuch balls, most of the mass is located away from the ball's axis ofrotation and thus more force is needed to generate spin. These ballshave a generally low spin rate as the ball leaves the club's face aftercontact between the ball and club. Such core structures (wherein thespecific gravity of the outer core is greater than the specific gravityof the inner core) is preferred in the present invention. Thus, in onepreferred embodiment, the concentration of mineral filler particulate isin the range of about 0.1 to about 9.0% by weight.

It is also recognized that other nano-sized materials may be added tothe foam formulation in accordance with this invention. For example,nano-sized particles may be added as described in Sullivan et al., U.S.Pat. No. 7,261,647, Rajagopalan et al., U.S. Pat. No. 7,314,896, andSullivan et al., U.S. Pat. No. 8,124,681, the disclosures of which arehereby incorporated by reference. Other nano-materials includesubstantially oriented nanostructures as disclosed in Morgan et al., USPatent Application Publication 2013/0072322, the disclosure of which ishereby incorporated by reference. These nanostructures include variousspherical, ovoid, elongated or branched structures, including, but notlimited to, nanocrystals, nanowires, nanofibers, nanorods, nanotubes,branched nanowires, nanotetrapods, nanotripods, nanobipods, nanodots,quantum dots, nanoparticles, nanoribbons, and the like.

Properties of Polyurethane Foams

The polyurethane foam compositions of this invention have numerouschemical and physical properties making them suitable for coreassemblies in golf balls. For example, there are properties relating tothe reaction of the isocyanate and polyol components and blowing agent,particularly “cream time,” “gel time,” “rise time,” “tack-free time,”and “free-rise density.” In general, cream time refers to the timeperiod from the point of mixing the raw ingredients together to thepoint where the mixture turns cloudy in appearance or changes color andbegins to rise from its initial stable state. Normally, the cream timeof the foam compositions of this invention is within the range of about20 to about 240 seconds. In general, gel time refers to the time periodfrom the point of mixing the raw ingredients together to the point wherethe expanded foam starts polymerizing/gelling. Rise time generallyrefers to the time period from the point of mixing the raw ingredientstogether to the point where the reacted foam has reached its largestvolume or maximum height. The rise time of the foam compositions of thisinvention typically is in the range of about 60 to about 360 seconds.Tack-free time generally refers to the time it takes for the reactedfoam to lose its tackiness, and the foam compositions of this inventionnormally have a tack-free time of about 60 to about 3600 seconds.Free-rise density refers to the density of the resulting foam when it isallowed to rise unrestricted without a cover or top being placed on themold.

The density of the foam is an important property and is defines as theweight per unit volume (typically, g/cm³) and can be measured per ASTMD-1622. The hardness, stiffness, and load-bearing capacity of the foamare independent of the foam's density, although foams having a highdensity typically have high hardness and stiffness. Normally, foamshaving higher densities have higher compression strength. Surprisingly,the foam compositions used to produce the inner core of the golf ballsper this invention have a relatively low density; however, the foams arenot necessarily soft and flexible, rather, they may be relatively firm,rigid, or semi-rigid depending upon the desired golf ball properties.Tensile strength, tear-resistance, and elongation generally refer to thefoam's ability to resist breaking or tearing, and these properties canbe measured per ASTM D-1623. The durability of foams is important,because introducing fillers and other additives into the foamcomposition can increase the tendency of the foam to break or tearapart. In general, the tensile strength of the foam compositions of thisinvention is in the range of about 20 to about 1000 psi (parallel to thefoam rise) and about 50 to about 1000 psi (perpendicular to the foamrise) as measured per ASTM D-1623 at 23° C. and 50% relative humidity(RH). Meanwhile, the flex modulus of the foams of this invention isgenerally in the range of about 5 to about 45 kPa as measured per ASTMD-790, and the foams generally have a compressive modulus of 200 to50,000 psi.

In another test, compression strength is measured on an Instron machineaccording to ASTM D-1621. The foam is cut into blocks and thecompression strength is measured as the force required to compress theblock by 10%. In general, the compressive strength of the foamcompositions of this invention is in the range of about 100 to about1800 psi (parallel and perpendicular to the foam rise) as measured perASTM D-1621 at 23° C. and 50% relative humidity (RH). The test isconducted perpendicular to the rise of the foam or parallel to the riseof the foam. The Percentage (%) of Compression Set also can be used.This is a measure of the permanent deformation of a foam sample after ithas been compressed between two metal plates under controlled time andtemperature condition (standard—22 hours at 70° C. (158° F.)). The foamis compressed to a thickness given as a percentage of its originalthickness that remained “set.” Preferably, the Compression Set of thefoam is less than ten percent (10%), that is, the foam recovers to apoint of 90% or greater of its original thickness.

Methods of Preparing the Foam Composition

The foam compositions of this invention may be prepared using differentmethods. In one preferred embodiment, the method involves preparing acastable composition comprising a reactive mixture of a polyisocyanate,polyol, water, curing agent, surfactant, and catalyst. A motorized mixercan be used to mix the starting ingredients together and form a reactiveliquid mixture. Alternatively, the ingredients can be manually mixedtogether. An exothermic reaction occurs when the ingredients are mixedtogether and this continues as the reactive mixture is dispensed intothe mold cavities (otherwise referred to as half-molds or mold cups).The mold cavities may be referred to as first and second, or upper andlower, mold cavities. The mold cavities preferably are made of metalsuch as, for example, brass or silicon bronze.

Referring to FIG. 2, the mold cavities are generally indicated at (9)and (10). The lower and upper mold cavities (9, 10) are placed in lowerand upper mold frame plates (11, 12). The frame plates (11, 12) containguide pins and complementary alignment holes (not shown in drawing). Theguide pins are inserted into the alignment holes to secure the lowerplate (11) to the upper plate (12). The lower and upper mold cavities(9, 10) are mated together as the frame plates (11, 12) are fastened.When the lower and upper mold cavities (9, 10) are joined together, theydefine an interior spherical cavity that houses the spherical core. Theupper mold contains a vent or hole (14) to allow for the expanding foamto fill the cavities uniformly. A secondary overflow chamber (16), whichis located above the vent (14), can be used to adjust the amount of foamoverflow and thus adjust the density of the core structure being moldedin the cavities. As the lower and upper mold cavities (9, 10) are matedtogether and sufficient heat and pressure is applied, the foamedcomposition cures and solidifies to form a relatively rigid andlightweight spherical core. The resulting cores are cooled and thenremoved from the mold.

Hardness of the Inner Core

As shown in FIG. 1, a foamed inner core (4) having a geometric center(6) and outer skin (8) may be prepared per the molding method discussedabove. The outer skin (8) is generally a non-foamed region that formsthe outer surface of the core structure. The resulting inner corepreferably has a diameter within a range of about 0.100 to about 1.100inches. For example, the inner core may have a diameter within a rangeof about 0.250 to about 1.000 inches. In another example, the inner coremay have a diameter within a range of about 0.300 to about 0.800 inches.More particularly, the inner core preferably has a diameter size with alower limit of about 0.10 or 0.12 or 0.15 or 0.25 or 0.30 or 0.35 or0.45 or 0.55 inches and an upper limit of about 0.60 or 0.65 or 0.70 or0.80 or 0.90 or 1.00 or 1.10 inches. The outer skin (8) of the innercore is relatively thin preferably having a thickness of less than about0.020 inches and more preferably less than 0.010 inches. In onepreferred embodiment, the foamed core has a “positive” hardness gradient(that is, the outer skin of the inner core is harder than its geometriccenter.)

For example, the geometric center hardness of the inner core(H_(inner core center)), as measured in Shore C units, is about 10 ShoreC or greater and preferably has a lower limit of about 10 or 16 or 20 or25 or 30 or 32 or 34 or 36 or 40 Shore C and an upper limit of about 42or 44 or 48 or 50 or 52 or 56 or 60 or 62 or 65 or 68 or 70 or 74 or 78or 80 Shore C. In one preferred version, the geometric center hardnessof the inner core (H_(inner core center)) is about 60 Shore C. When aflexible, relatively soft foam is used, the foam may have a Shore Ahardness of about 10 or greater, and preferably has a lower limit of 15,20, 25, 30, or 35 Shore A and an upper limit of about 60, 65, 70, 80,85, or 90 Shore A. In one preferred embodiment, the geometric centerhardness of the inner core is about 55 Shore A. TheH_(inner core center), as measured in Shore D units, is about 15 Shore Dor greater and more preferably within a range having a lower limit ofabout 15 or 18 or 20 or 22 or 25 or 28 or 30 or 32 or 36 or 40 or 44Shore D and an upper limit of about 45 or 48 or 50 or 52 or 55 or 58 or60 or 62 or 64 or 66 or 70 or 72 or 74 or 78 or 80 or 82 or 84 or 88 or90 Shore D. Meanwhile, the outer surface hardness of the inner core(H_(inner core surface)), as measured in Shore C, is about 20 Shore C orgreater and preferably has a lower limit of about 13 or 17 or 20 or 22or 24 or 28 or 30 or 32 or 35 or 36 or 40 or 42 or 44 or 48 or 50 ShoreC and an upper limit of about 52 or 55 or 58 or 60 or 62 or 64 or 66 or70 or 74 or 78 or 80 or 86 or 88 or 90 or 92 or 95 Shore C. The outersurface hardness of the inner core ((H_(inner core surface)), asmeasured in Shore D units, preferably has a lower limit of about 25 or28 or 30 or 32 or 36 or 40 or 44 Shore D and an upper limit of about 45or 48 or 50 or 52 or 55 or 58 or 60 or 62 or 64 or 66 or 70 or 74 or 78or 80 or 82 or 84 or 88 or 90 or 94 or 96 Shore D.

Density of the Inner Core

The foamed inner core preferably has a specific gravity of about 0.25 toabout 1.25 g/cc. That is, the density of the inner core (as measured atany point of the inner core structure) is preferably within the range ofabout 0.25 to about 1.25 g/cc. By the term, “specific gravity of theinner core” (“SG_(inner)”), it is generally meant the specific gravityof the inner core as measured at any point of the inner core structure.It should be understood, however, that the specific gravity values, astaken at different points of the inner core structure, may vary. Forexample, the foamed inner core may have a “positive” density gradient(that is, the outer surface (skin) of the inner core may have a densitygreater than the geometric center of the inner core.) In one preferredversion, the specific gravity of the geometric center of the inner core(SG_(center of inner core)) is less than 1.00 g/cc and more preferably0.90 g/cc or less. More particularly, in one version, the(SG_(center of inner core)) is in the range of about 0.10 to about 0.90g/cc. For example, the (SG_(center of inner core)) may be within a rangehaving a lower limit of about 0.10 or 0.15 of 0.20 or 0.24 or 0.30 or0.35 or 0.37 or 0.40 or 0.42 or 0.45 or 0.47 or 0.50 and an upper limitof about 0.60 or 0.65 or 0.70 or 0.74 or 0.78 or 0.80, or 0.82 or 0.84or 0.85 or 0.88 or 0.90 g/cc. Meanwhile, the specific gravity of theouter surface (skin) of the inner core (SG_(skin of inner core)), in onepreferred version, is greater than about 0.90 g/cc and more preferablygreater than 1.00 g/cc. For example, the (SG_(skin of inner core)) mayfall within the range of about 0.90 to about 2.00. More particularly, inone version, the (SG_(skin of inner core)) may have a specific gravitywith a lower limit of about 0.90 or 0.92 or 0.95 or 0.98 or 1.00 or 1.02or 1.06 or 1.10 or 1.12 or 1.15 or 1.18 and an upper limit of about 1.20or 1.24 or 1.30 or 1.32 or 1.35 or 1.38 or 1.40 or 1.44 or 1.50 or 1.60or 1.65 or 1.70 or 1.76 or 1.80 or 1.90 or 1.92 or 2.00. In otherinstances, the outer skin may have a specific gravity of less than 0.90g/cc. For example, the specific gravity of the outer skin(SG_(skin of inner core)) may be about 0.75 or 0.80 or 0.82 or 0.85 or0.88 g/cc. In such instances, wherein both the(SG_(center of inner core)) and (SG_(skin of inner core)) are less than0.90 g/cc, it is still preferred that the(SG_(center of inner core))_(is) less than the(SG_(skin of inner core)).

Polyisocyanates and Polyols for Making the Polyurethane Foams

As discussed above, in one preferred embodiment, a foamed polyurethanecomposition is used to form the inner core. In general, the polyurethanecompositions contain urethane linkages formed by reacting an isocyanategroup (—N═C═O) with a hydroxyl group (OH). The polyurethanes areproduced by the reaction of multi-functional isocyanates containing twoor more isocyanate groups with a polyol having two or more hydroxylgroups. The formulation may also contain a catalyst, surfactant, andother additives.

In particular, the foam inner core of this invention may be preparedfrom a composition comprising an aromatic polyurethane, which ispreferably formed by reacting an aromatic diisocyanate with a polyol.Suitable aromatic diisocyanates that may be used in accordance with thisinvention include, for example, toluene 2,4-diisocyanate (TDI), toluene2,6-diisocyanate (TDI), 4,4′-methylene diphenyl diisocyanate (MDI),2,4′-methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyldiisocyanate (PMDI), p-phenylene diisocyanate (PPDI), m-phenylenediisocyanate (PDI), naphthalene 1,5-diisocyanate (NDI), naphthalene2,4-diisocyanate (NDI), p-xylene diisocyanate (XDI), and homopolymersand copolymers and blends thereof. The aromatic isocyanates are able toreact with the hydroxyl or amine compounds and form a durable and toughpolymer having a high melting point. The resulting polyurethanegenerally has good mechanical strength and tear-resistance.

Alternatively, the foamed composition of the inner core may be preparedfrom a composition comprising aliphatic polyurethane, which ispreferably formed by reacting an aliphatic diisocyanate with a polyol.Suitable aliphatic diisocyanates that may be used in accordance withthis invention include, for example, isophorone diisocyanate (IPDI),1,6-hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethanediisocyanate (“H₁₂ MDI”), meta-tetramethylxylyene diisocyanate (TMXDI),trans-cyclohexane diisocyanate (CHDI),1,3-bis(isocyanatomethyl)cyclohexane;1,4-bis(isocyanatomethyl)cyclohexane; and homopolymers and copolymersand blends thereof. The resulting polyurethane generally has good lightand thermal stability. Preferred polyfunctional isocyanates include4,4′-methylene diphenyl diisocyanate (MDI), 2,4′-methylene diphenyldiisocyanate (MDI), and polymeric MDI having a functionality in therange of 2.0 to 3.5 and more preferably 2.2 to 2.5.

Any suitable polyol may be used to react with the polyisocyanate inaccordance with this invention. Exemplary polyols include, but are notlimited to, polyether polyols, hydroxy-terminated polybutadiene(including partially/fully hydrogenated derivatives), polyester polyols,polycaprolactone polyols, and polycarbonate polyols. In one preferredembodiment, the polyol includes polyether polyol. Examples include, butare not limited to, polytetramethylene ether glycol (PTMEG),polyethylene propylene glycol, polyoxypropylene glycol, and mixturesthereof. The hydrocarbon chain can have saturated or unsaturated bondsand substituted or unsubstituted aromatic and cyclic groups. Preferably,the polyol of the present invention includes PTMEG.

As discussed further below, chain extenders (curing agents) are added tothe mixture to build-up the molecular weight of the polyurethanepolymer. In general, hydroxyl-terminated curing agents, amine-terminatedcuring agents, and mixtures thereof are used.

A catalyst may be employed to promote the reaction between theisocyanate and polyol compounds. Suitable catalysts include, but are notlimited to, bismuth catalyst; zinc octoate; tin catalysts such asbis-butyltin dilaurate, bis-butyltin diacetate, stannous octoate; tin(II) chloride, tin (IV) chloride, bis-butyltin dimethoxide,dimethyl-bis[1-oxonedecyl)oxy]stannane, di-n-octyltin bis-isooctylmercaptoacetate; amine catalysts such as triethylenediamine,triethylamine, tributylamine, 1,4-diaza(2,2,2)bicyclooctane,tetramethylbutane diamine, bis[2-dimethylaminoethyl]ether,N,N-dimethylaminopropylamine, N,N-dimethylcyclohexylamine,N,N,N′,N′,N″-pentamethyldiethylenetriamine, diethanolamine,dimethtlethanolamine, N-[2-(dimethylamino)ethyl]-N-methylethanolamine,N-ethylmorpholine, 3-dimethylamino-N,N-dimethylpropionamide, andN,N′,N″-dimethylaminopropylhexahydrotriazine; organic acids such asoleic acid and acetic acid; delayed catalysts; and mixtures thereof.Zirconium-based catalysts such as, for example, bis(2-dimethylaminoethyl) ether; mixtures of zinc complexes and amine compounds suchas KKAT™ XK 614, available from King Industries; and amine catalystssuch as Niax™ A-2 and A-33, available from Momentive SpecialtyChemicals, Inc. are particularly preferred. The catalyst is preferablyadded in an amount sufficient to catalyze the reaction of the componentsin the reactive mixture. In one embodiment, the catalyst is present inan amount from about 0.001 percent to about 1 percent, and preferably0.1 to 0.5 percent, by weight of the composition.

In one preferred embodiment, as described above, water is used as thefoaming agent—the water reacts with the polyisocyanate compound(s) andforms carbon dioxide gas which induces foaming of the mixture. Thereaction rate of the water and polyisocyanate compounds affects howquickly the foam is formed as measured per reaction profile propertiessuch as cream time, gel time, and rise time of the foam.

The hydroxyl chain-extending (curing) agents are preferably selectedfrom the group consisting of ethylene glycol; diethylene glycol;polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol;2-methyl-1,4-butanediol; monoethanolamine; diethanolamine;triethanolamine; monoisopropanolamine; diisopropanolamine; dipropyleneglycol; polypropylene glycol; 1,2-butanediol; 1,3-butanediol;1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol;trimethylolpropane; cyclohexyldimethylol; triisopropanolamine;N,N,N′,N′-tetra-(2-hydroxypropyl)-ethylene diamine; diethylene glycolbis-(aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol;1,3-bis-(2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol;1,3-bis-[2-(2-hydroxyethoxy) ethoxy]cyclohexane;1,3-bis-{2-[2-(2-hydroxyethoxy) ethoxy]ethoxy}cyclohexane;trimethylolpropane; polytetramethylene ether glycol (PTMEG), preferablyhaving a molecular weight from about 250 to about 3900; and mixturesthereof. Di, tri, and tetra-functional polycaprolactone diols such as,2-oxepanone polymer initiated with 1,4-butanediol,2-ethyl-2-(hydroxymethyl)-1,3-propanediol, or2,2-bis(hydroxymethyl)-1,3-propanediolsuch, may be used.

Suitable amine chain-extending (curing) agents that can be used inchain-extending the polyurethane prepolymer include, but are not limitedto, unsaturated diamines such as 4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-dianiline or “MDA”), m-phenylenediamine,p-phenylenediamine, 1,2- or 1,4-bis(sec-butylamino)benzene,3,5-diethyl-(2,4- or 2,6-) toluenediamine or “DETDA”,3,5-dimethylthio-(2,4- or 2,6-)toluenediamine, 3,5-diethylthio-(2,4- or2,6-)toluenediamine, 3,3′-dimethyl-4,4′-diamino-diphenylmethane,3,3′-diethyl-5,5′-dimethyl4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(2-ethyl-6-methyl-benezeneamine)),3,3′-dichloro-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(2-chloroaniline) or “MOCA”),3,3′,5,5′-tetraethyl-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(2,6-diethylaniline),2,2′-dichloro-3,3′,5,5′-tetraethyl-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(3-chloro-2,6-diethyleneaniline) or “MCDEA”),3,3′-diethyl-5,5′-dichloro-4,4′-diamino-diphenylmethane, or “MDEA”),3,3′-dichloro-2,2′,6,6′-tetraethyl-4,4′-diamino-diphenylmethane,3,3′-dichloro-4,4′-diamino-diphenylmethane,4,4′-methylene-bis(2,3-dichloroaniline) (i.e.,2,2′,3,3′-tetrachloro-4,4′-diamino-diphenylmethane or “MDCA”),4,4′-bis(sec-butylamino)-diphenylmethane,N,N′-dialkylamino-diphenylmethane,trimethyleneglycol-di(p-aminobenzoate),polyethyleneglycol-di(p-aminobenzoate),polytetramethyleneglycol-di(p-aminobenzoate); saturated diamines such asethylene diamine, 1,3-propylene diamine, 2-methyl-pentamethylenediamine, hexamethylene diamine, 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine, imino-bis(propylamine), imido-bis(propylamine),methylimino-bis(propylamine) (i.e.,N-(3-aminopropyl)-N-methyl-1,3-propanediamine),1,4-bis(3-aminopropoxy)butane (i.e.,3,3′-[1,4-butanediylbis-(oxy)bis]-1-propanamine),diethyleneglycol-bis(propylamine) (i.e.,diethyleneglycol-di(aminopropyl)ether),4,7,10-trioxatridecane-1,13-diamine, 1-methyl-2,6-diamino-cyclohexane,1,4-diamino-cyclohexane, poly(oxyethylene-oxypropylene) diamines, 1,3-or 1,4-bis(methylamino)-cyclohexane, isophorone diamine, 1,2- or1,4-bis(sec-butylamino)-cyclohexane, N,N′-diisopropyl-isophoronediamine, 4,4′-diamino-dicyclohexylmethane,3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane,3,3′-dichloro-4,4′-diamino-dicyclohexylmethane,N,N′-dialkylamino-dicyclohexylmethane, polyoxyethylene diamines,3,3′-diethyl-5,5′-dimethyl-4,4′-diamino-dicyclohexylmethane,polyoxypropylene diamines,3,3′-diethyl-5,5′-dichloro-4,4′-diamino-dicyclohexylmethane,polytetramethylene ether diamines,3,3′,5,5′-tetraethyl-4,4′-diamino-dicyclohexylmethane (i.e.,4,4′-methylene-bis(2,6-diethylaminocyclohexane)),3,3′-dichloro-4,4′-diamino-dicyclohexylmethane,2,2′-dichloro-3,3′,5,5′-tetraethyl-4,4′-diamino-dicyclohexylmethane,(ethylene oxide)-capped polyoxypropylene ether diamines,2,2′,3,3′-tetrachloro-4,4′-diamino-dicyclohexylmethane,4,4′-bis(sec-butylamino)-dicyclohexylmethane; triamines such asdiethylene triamine, dipropylene triamine, (propylene oxide)-basedtriamines (i.e., polyoxypropylene triamines),N-(2-aminoethyl)-1,3-propylenediamine (i.e., N₃-amine), glycerin-basedtriamines, (all saturated); tetramines such asN,N′-bis(3-aminopropyl)ethylene diamine (i.e., N₄-amine) (bothsaturated), triethylene tetramine; and other polyamines such astetraethylene pentamine (also saturated). One suitable amine-terminatedchain-extending agent is Ethacure 300™ (dimethylthiotoluenediamine or amixture of 2,6-diamino-3,5-dimethylthiotoluene and2,4-diamino-3,5-dimethylthiotoluene.) The amine curing agents used aschain extenders normally have a cyclic structure and a low molecularweight (250 or less).

When a hydroxyl-terminated curing agent is used, the resultingpolyurethane composition contains urethane linkages. On the other hand,when an amine-terminated curing agent is used, any excess isocyanategroups will react with the amine groups in the curing agent. Theresulting polyurethane composition contains urethane and urea linkagesand may be referred to as a polyurethane/urea hybrid.

Two-Layered Cores

As discussed above, the inner core (center) is made preferably from afoamed composition. Preferably, a two-layered or dual-core is made,wherein the inner core is surrounded by an outer core layer. In onepreferred embodiment, the outer core layer is formed from a non-foamedthermoset composition and more preferably from a non-foamed thermosetrubber composition.

Suitable thermoset rubber materials that may be used to form the outercore layer include, but are not limited to, polybutadiene, polyisoprene,ethylene propylene rubber (“EPR”), ethylene-propylene-diene (“EPDM”)rubber, styrene-butadiene rubber, styrenic block copolymer rubbers (suchas “SI”, “SIS”, “SB”, “SBS”, “SIBS”, and the like, where “S” is styrene,“I” is isobutylene, and “B” is butadiene), polyalkenamers such as, forexample, polyoctenamer, butyl rubber, halobutyl rubber, polystyreneelastomers, polyethylene elastomers, polyurethane elastomers, polyureaelastomers, metallocene-catalyzed elastomers and plastomers, copolymersof isobutylene and p-alkylstyrene, halogenated copolymers of isobutyleneand p-alkylstyrene, copolymers of butadiene with acrylonitrile,polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber,acrylonitrile chlorinated isoprene rubber, and blends of two or morethereof. Preferably, the outer core layer is formed from a polybutadienerubber composition.

The thermoset rubber composition may be cured using conventional curingprocesses. Suitable curing processes include, for example,peroxide-curing, sulfur-curing, high-energy radiation, and combinationsthereof. Preferably, the rubber composition contains a free-radicalinitiator selected from organic peroxides, high energy radiation sourcescapable of generating free-radicals, and combinations thereof. In onepreferred version, the rubber composition is peroxide-cured. Suitableorganic peroxides include, but are not limited to, dicumyl peroxide;n-butyl-4,4-di(t-butylperoxy) valerate;1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane;2,5-dimethyl-2,5-di(t-butylperoxy) hexane; di-t-butyl peroxide;di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide;2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3;di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoylperoxide; t-butyl hydroperoxide; and combinations thereof. In aparticular embodiment, the free radical initiator is dicumyl peroxide,including, but not limited to Perkadox® BC, commercially available fromAkzo Nobel. Peroxide free-radical initiators are generally present inthe rubber composition in an amount of at least 0.05 parts by weight per100 parts of the total rubber, or an amount within the range having alower limit of 0.05 parts or 0.1 parts or 1 part or 1.25 parts or 1.5parts or 2.5 parts or 5 parts by weight per 100 parts of the totalrubbers, and an upper limit of 2.5 parts or 3 parts or 5 parts or 6parts or 10 parts or 15 parts by weight per 100 parts of the totalrubber. Concentrations are in parts per hundred (phr) unless otherwiseindicated. As used herein, the term, “parts per hundred,” also known as“phr” or “pph” is defined as the number of parts by weight of aparticular component present in a mixture, relative to 100 parts byweight of the polymer component. Mathematically, this can be expressedas the weight of an ingredient divided by the total weight of thepolymer, multiplied by a factor of 100.

The rubber compositions may further include a reactive cross-linkingco-agent. Suitable co-agents include, but are not limited to, metalsalts of unsaturated carboxylic acids having from 3 to 8 carbon atoms;unsaturated vinyl compounds and polyfunctional monomers (e.g.,trimethylolpropane trimethacrylate); phenylene bismaleimide; andcombinations thereof. Particular examples of suitable metal saltsinclude, but are not limited to, one or more metal salts of acrylates,diacrylates, methacrylates, and dimethacrylates, wherein the metal isselected from magnesium, calcium, zinc, aluminum, lithium, and nickel.In a particular embodiment, the co-agent is selected from zinc salts ofacrylates, diacrylates, methacrylates, and dimethacrylates. In anotherparticular embodiment, the agent is zinc diacrylate (ZDA). When theco-agent is zinc diacrylate and/or zinc dimethacrylate, the co-agent istypically included in the rubber composition in an amount within therange having a lower limit of 1 or 5 or 10 or 15 or 19 or 20 parts byweight per 100 parts of the total rubber, and an upper limit of 24 or 25or 30 or 35 or 40 or 45 or 50 or 60 parts by weight per 100 parts of thebase rubber.

Radical scavengers such as a halogenated organosulfur, organicdisulfide, or inorganic disulfide compounds may be added to the rubbercomposition. These compounds also may function as “soft and fastagents.” As used herein, “soft and fast agent” means any compound or ablend thereof that is capable of making a core: 1) softer (having alower compression) at a constant “coefficient of restitution” (COR);and/or 2) faster (having a higher COR at equal compression), whencompared to a core equivalently prepared without a soft and fast agent.Preferred halogenated organosulfur compounds include, but are notlimited to, pentachlorothiophenol (PCTP) and salts of PCTP such as zincpentachlorothiophenol (ZnPCTP). Using PCTP and ZnPCTP in golf ball innercores helps produce softer and faster inner cores. The PCTP and ZnPCTPcompounds help increase the resiliency and the coefficient ofrestitution of the core. In a particular embodiment, the soft and fastagent is selected from ZnPCTP, PCTP, ditolyl disulfide, diphenyldisulfide, dixylyl disulfide, 2-nitroresorcinol, and combinationsthereof.

The rubber composition also may include filler(s) such as materialsselected from carbon black, clay and nanoclay particles as discussedabove, talc (e.g., Luzenac HAR® high aspect ratio talcs, commerciallyavailable from Luzenac America, Inc.), glass (e.g., glass flake, milledglass, and microglass), mica and mica-based pigments (e.g., Iriodin®pearl luster pigments, commercially available from The Merck Group), andcombinations thereof. Metal fillers such as, for example, particulate;powders; flakes; and fibers of copper, steel, brass, tungsten, titanium,aluminum, magnesium, molybdenum, cobalt, nickel, iron, lead, tin, zinc,barium, bismuth, bronze, silver, gold, and platinum, and alloys andcombinations thereof also may be added to the rubber composition toadjust the specific gravity of the composition as needed. As discussedfurther below, in one preferred embodiment, the specific gravity of theinner core layer (for example, foamed polyurethane) has a specificgravity less than the outer core layer (for example, polybutadienerubber). In such an event, if mineral, metal, or other fillers are addedto the polybutadiene rubber composition used to form the outer core, itis important the concentration of such fillers be sufficient so that thespecific gravity of the outer core layer is greater than the specificgravity of the inner core. For example, the concentration of the fillersmay be in an amount of at least about 5% by weight based on total weightof composition

In addition, the rubber compositions may include antioxidants to preventthe breakdown of the elastomers. Also, processing aids such as highmolecular weight organic acids and salts thereof may be added to thecomposition. Suitable organic acids are aliphatic organic acids,aromatic organic acids, saturated mono-functional organic acids,unsaturated monofunctional organic acids, multi-unsaturatedmono-functional organic acids, and dimerized derivatives thereof.Particular examples of suitable organic acids include, but are notlimited to, caproic acid, caprylic acid, capric acid, lauric acid,stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid,myristic acid, benzoic acid, palmitic acid, phenylacetic acid,naphthalenoic acid, and dimerized derivatives thereof. The organic acidsare aliphatic, mono-functional (saturated, unsaturated, ormulti-unsaturated) organic acids. Salts of these organic acids may alsobe employed. The salts of organic acids include the salts of barium,lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium,strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver,aluminum, tin, or calcium, salts of fatty acids, particularly stearic,behenic, erucic, oleic, linoelic or dimerized derivatives thereof. It ispreferred that the organic acids and salts of the present invention berelatively non-migratory (they do not bloom to the surface of thepolymer under ambient temperatures) and non-volatile (they do notvolatilize at temperatures required for melt-blending.) Otheringredients such as accelerators (for example, tetra methylthiuram),processing aids, dyes and pigments, wetting agents, surfactants,plasticizers, coloring agents, fluorescent agents, chemical blowing andfoaming agents, defoaming agents, stabilizers, softening agents, impactmodifiers, antiozonants, as well as other additives known in the art maybe added to the rubber composition.

Examples of commercially-available polybutadiene rubbers that can beused in accordance with this invention, include, but are not limited to,BR 01 and BR 1220, available from BST Elastomers of Bangkok, Thailand;SE BR 1220LA and SE BR1203, available from DOW Chemical Co of Midland,Mich.; BUDENE 1207, 1207s, 1208, and 1280 available from Goodyear, Incof Akron, Ohio; BR 01, 51 and 730, available from Japan Synthetic Rubber(JSR) of Tokyo, Japan; BUNA CB 21, CB 22, CB 23, CB 24, CB 25, CB 29MES, CB 60, CB Nd 60, CB 55 NF, CB 70 B, CB KA 8967, and CB 1221,available from Lanxess Corp. of Pittsburgh. Pa.; BR1208, available fromLG Chemical of Seoul, South Korea; UBEPOL BR130B, BR150, BR150B, BR150L,BR230, BR360L, BR710, and VCR617, available from UBE Industries, Ltd. ofTokyo, Japan; EUROPRENE NEOCIS BR 60, INTENE 60 AF and P30AF, andEUROPRENE BR HV80, available from Polimeri Europa of Rome, Italy; AFDENE50 and NEODENE BR40, BR45, BR50 and BR60, available from Karbochem (PTY)Ltd. of Bruma, South Africa; KBR 01, NdBr 40, NdBR-45, NdBr 60, KBR710S, KBR 710H, and KBR 750, available from Kumho Petrochemical Co.,Ltd. Of Seoul, South Korea; DIENE 55NF, 70AC, and 320 AC, available fromFirestone Polymers of Akron, Ohio; and PBR-Nd Group II and Group III,available from Nizhnekamskneftekhim, Inc. of Nizhnekamsk, TartarstanRepublic.

The polybutadiene rubber is used in an amount of at least about 5% byweight based on total weight of composition and is generally present inan amount of about 5% to about 100%, or an amount within a range havinga lower limit of 5% or 10% or 20% or 30% or 40% or 50% and an upperlimit of 55% or 60% or 70% or 80% or 90% or 95% or 100%. Preferably, theconcentration of polybutadiene rubber is about 40 to about 95 weightpercent. If desirable, lesser amounts of other thermoset materials maybe incorporated into the base rubber. Such materials include the rubbersdiscussed above, for example, cis-polyisoprene, trans-polyisoprene,balata, polychloroprene, polynorbornene, polyoctenamer, polypentenamer,butyl rubber, EPR, EPDM, styrene-butadiene, and the like.

In alternative embodiments, the outer core layer may comprise athermoplastic material, for example, an ionomer composition containingacid groups that are at least partially-neutralized. Suitable ionomercompositions include partially-neutralized ionomers andhighly-neutralized ionomers (HNPs), including ionomers formed fromblends of two or more partially-neutralized ionomers, blends of two ormore highly-neutralized ionomers, and blends of one or morepartially-neutralized ionomers with one or more highly-neutralizedionomers. For purposes of the present disclosure, “HNP” refers to anacid copolymer after at least 70% of all acid groups present in thecomposition are neutralized. Preferred ionomers are salts of O/X- andO/X/Y-type acid copolymers, wherein O is an α-olefin, X is a C₃-C₈α,β-ethylenically unsaturated carboxylic acid, and Y is a softeningmonomer. O is preferably selected from ethylene and propylene. X ispreferably selected from methacrylic acid, acrylic acid, ethacrylicacid, crotonic acid, and itaconic acid. Methacrylic acid and acrylicacid are particularly preferred. Y is preferably selected from (meth)acrylate and alkyl (meth) acrylates wherein the alkyl groups have from 1to 8 carbon atoms, including, but not limited to, n-butyl (meth)acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, and ethyl(meth) acrylate.

Preferred O/X and O/X/Y-type copolymers include, without limitation,ethylene acid copolymers, such as ethylene/(meth)acrylic acid,ethylene/(meth)acrylic acid/maleic anhydride, ethylene/(meth)acrylicacid/maleic acid mono-ester, ethylene/maleic acid, ethylene/maleic acidmono-ester, ethylene/(meth)acrylic acid/n-butyl (meth)acrylate,ethylene/(meth)acrylic acid/iso-butyl (meth)acrylate,ethylene/(meth)acrylic acid/methyl (meth)acrylate,ethylene/(meth)acrylic acid/ethyl (meth)acrylate terpolymers, and thelike. The term, “copolymer,” as used herein, includes polymers havingtwo types of monomers, those having three types of monomers, and thosehaving more than three types of monomers. Preferred α,β-ethylenicallyunsaturated mono- or dicarboxylic acids are (meth) acrylic acid,ethacrylic acid, maleic acid, crotonic acid, fumaric acid, itaconicacid. (Meth) acrylic acid is most preferred. As used herein, “(meth)acrylic acid” means methacrylic acid and/or acrylic acid. Likewise,“(meth) acrylate” means methacrylate and/or acrylate.

In a particularly preferred version, highly neutralized E/X- andE/X/Y-type acid copolymers, wherein E is ethylene, X is a C₃-C₈α,β-ethylenically unsaturated carboxylic acid, and Y is a softeningmonomer are used. X is preferably selected from methacrylic acid,acrylic acid, ethacrylic acid, crotonic acid, and itaconic acid.Methacrylic acid and acrylic acid are particularly preferred. Y ispreferably an acrylate selected from alkyl acrylates and aryl acrylatesand preferably selected from (meth) acrylate and alkyl (meth) acrylateswherein the alkyl groups have from 1 to 8 carbon atoms, including, butnot limited to, n-butyl (meth) acrylate, isobutyl (meth) acrylate,methyl (meth) acrylate, and ethyl (meth) acrylate. Preferred E/X/Y-typecopolymers are those wherein X is (meth) acrylic acid and/or Y isselected from (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. Morepreferred E/X/Y-type copolymers are ethylene/(meth) acrylic acid/n-butylacrylate, ethylene/(meth) acrylic acid/methyl acrylate, andethylene/(meth) acrylic acid/ethyl acrylate.

The amount of ethylene in the acid copolymer is typically at least 15wt. %, preferably at least 25 wt. %, more preferably least 40 wt. %, andeven more preferably at least 60 wt. %, based on total weight of thecopolymer. The amount of C₃ to C₈ α,β-ethylenically unsaturated mono- ordicarboxylic acid in the acid copolymer is typically from 1 wt. % to 35wt. %, preferably from 5 wt. % to 30 wt. %, more preferably from 5 wt. %to 25 wt. %, and even more preferably from 10 wt. % to 20 wt. %, basedon total weight of the copolymer. The amount of optional softeningcomonomer in the acid copolymer is typically from 0 wt. % to 50 wt. %,preferably from 5 wt. % to 40 wt. %, more preferably from 10 wt. % to 35wt. %, and even more preferably from 20 wt. % to 30 wt. %, based ontotal weight of the copolymer. “Low acid” and “high acid” ionomericpolymers, as well as blends of such ionomers, may be used. In general,low acid ionomers are considered to be those containing 16 wt. % or lessof acid moieties, whereas high acid ionomers are considered to be thosecontaining greater than 16 wt. % of acid moieties.

The various O/X, E/X, O/X/Y, and E/X/Y-type copolymers are at leastpartially neutralized with a cation source, optionally in the presenceof a high molecular weight organic acid, such as those disclosed in U.S.Pat. No. 6,756,436, the entire disclosure of which is herebyincorporated herein by reference. The acid copolymer can be reacted withthe optional high molecular weight organic acid and the cation sourcesimultaneously, or prior to the addition of the cation source. Suitablecation sources include, but are not limited to, metal ion sources, suchas compounds of alkali metals, alkaline earth metals, transition metals,and rare earth elements; ammonium salts and monoamine salts; andcombinations thereof. Preferred cation sources are compounds ofmagnesium, sodium, potassium, cesium, calcium, barium, manganese,copper, zinc, lead, tin, aluminum, nickel, chromium, lithium, and rareearth metals.

Other suitable thermoplastic polymers that may be used to form the outercore layer include, but are not limited to, the following polymers(including homopolymers, copolymers, and derivatives thereof.)

(a) polyesters, particularly those modified with a compatibilizing groupsuch as sulfonate or phosphonate, including modified poly(ethyleneterephthalate), modified poly(butylene terephthalate), modifiedpoly(propylene terephthalate), modified poly(trimethyleneterephthalate), modified poly(ethylene naphthenate), and those disclosedin U.S. Pat. Nos. 6,353,050, 6,274,298, and 6,001,930, the entiredisclosures of which are hereby incorporated herein by reference, andblends of two or more thereof;

(b) polyamides, polyamide-ethers, and polyamide-esters, and thosedisclosed in U.S. Pat. Nos. 6,187,864, 6,001,930, and 5,981,654, theentire disclosures of which are hereby incorporated herein by reference,and blends of two or more thereof;

(c) polyurethanes, polyureas, polyurethane-polyurea hybrids, and blendsof two or more thereof;

(d) fluoropolymers, such as those disclosed in U.S. Pat. Nos. 5,691,066,6,747,110 and 7,009,002, the entire disclosures of which are herebyincorporated herein by reference, and blends of two or more thereof;

(e) polystyrenes, such as poly(styrene-co-maleic anhydride),acrylonitrile-butadiene-styrene, poly(styrene sulfonate), polyethylenestyrene, and blends of two or more thereof;

(f) polyvinyl chlorides and grafted polyvinyl chlorides, and blends oftwo or more thereof;

(g) polycarbonates, blends ofpolycarbonate/acrylonitrile-butadiene-styrene, blends ofpolycarbonate/polyurethane, blends of polycarbonate/polyester, andblends of two or more thereof;

(h) polyethers, such as polyarylene ethers, polyphenylene oxides, blockcopolymers of alkenyl aromatics with vinyl aromatics and polyamicesters,and blends of two or more thereof;

(i) polyimides, polyetherketones, polyamideimides, and blends of two ormore thereof; and

(j) polycarbonate/polyester copolymers and blends.

It also is recognized that thermoplastic materials can be “converted”into thermoset materials by cross-linking the polymer chains so theyform a network structure, and such cross-linked thermoplastic materialsmay be used to form the core layers in accordance with this invention.For example, thermoplastic polyolefins such as linear low densitypolyethylene (LLDPE), low density polyethylene (LDPE), and high densitypolyethylene (HDPE) may be cross-linked to form bonds between thepolymer chains. The cross-linked thermoplastic material typically hasimproved physical properties and strength over non-cross-linkedthermoplastics, particularly at temperatures above the crystallinemelting point. Preferably a partially or fully-neutralized ionomer, asdescribed above, is covalently cross-linked to render it into athermoset composition (that is, it contains at least some level ofcovalent, irreversable cross-links). Thermoplastic polyurethanes andpolyureas also may be converted into thermoset materials in accordancewith the present invention.

The cross-linked thermoplastic material may be created by exposing thethermoplastic to: 1) a high-energy radiation treatment, such as electronbeam or gamma radiation, such as disclosed in U.S. Pat. No. 5,891,973,which is incorporated by reference herein, 2) lower energy radiation,such as ultra-violet (UV) or infra-red (IR) radiation; 3) a solutiontreatment, such as an isocyanate or a silane; 4) incorporation ofadditional free radical initiator groups in the thermoplastic prior tomolding; and/or 5) chemical modification, such as esterification orsaponification, to name a few.

Modifications in thermoplastic polymeric structure of thermoplastic canbe induced by a number of methods, including exposing the thermoplasticmaterial to high-energy radiation or through a chemical process usingperoxide. Radiation sources include, but are not limited to, gamma-rays,electrons, neutrons, protons, x-rays, helium nuclei, or the like. Gammaradiation, typically using radioactive cobalt atoms and allows forconsiderable depth of treatment, if necessary. For core layers requiringlower depth of penetration, electron-beam accelerators or UV and IRlight sources can be used. Useful UV and IR irradiation methods aredisclosed in U.S. Pat. Nos. 6,855,070 and 7,198,576, which areincorporated herein by reference. The thermoplastic core layers may beirradiated at dosages greater than 0.05 Mrd, preferably ranging from 1Mrd to 20 Mrd, more preferably from 2 Mrd to 15 Mrd, and most preferablyfrom 4 Mrd to 10 Mrd. In one preferred embodiment, the cores areirradiated at a dosage from 5 Mrd to 8 Mrd and in another preferredembodiment, the cores are irradiated with a dosage from 0.05 Mrd to 3Mrd, more preferably 0.05 Mrd to 1.5 Mrd.

For example, a core assembly having a thermoplastic layer may beconverted to a thermoset layer by placing the core assembly on a slowlymove along a channel. Radiation from a radiation source, such as gammarays, is allowed to contact the surface of the cores. The source ispositioned to provide a generally uniform dose of radiation to the coresas they roll along the channel. The speed of the cores as they passthrough the radiation source is easily controlled to ensure the coresreceive sufficient dosage to create the desired hardness gradient. Thecores are irradiated with a dosage of 1 or more Mrd, more preferably 2Mrd to 15 Mrd. The intensity of the dosage is typically in the range of1 MeV to 20 MeV. For thermoplastic resins having a reactive group (e.g.,ionomers, thermoplastic urethanes, and the like), treating thethermoplastic core layer in a chemical solution of an isocyanate or anamine affects cross-linking and provides a harder surface and subsequenthardness gradient. Incorporation of peroxide or other free-radicalinitiator in the thermoplastic polymer, prior to molding or forming,also allows for heat curing on the molded core layer to create thedesired hardness gradient. By proper selection of time/temperature, anannealing process can be used to create a gradient. Suitable annealingand/or peroxide (free radical) methods are such as disclosed in U.S.Pat. Nos. 5,274,041 and 5,356,941, respectively, which are incorporatedby reference herein. Additionally, silane or amino-silane crosslinkingmay also be employed as disclosed in U.S. Pat. No. 7,279,529, thedisclosure of which incorporated herein by reference. The core layer maybe chemically treated in a solution, such as a solution containing oneor more isocyanates, to form the desired “positive hardness gradient.”The cores are typically exposed to the solution containing theisocyanate by immersing them in a bath at a particular temperature for agiven time. Exposure time should be greater than 1 minute, preferablyfrom 1 minute to 120 minutes, more preferably 5 minutes to 90 minutes,and most preferably 10 minutes to 60 minutes. In one preferredembodiment, the cores are immersed in the treating solution from 15minutes to 45 minutes, more preferably from 20 minutes to 40 minutes,and most preferably from 25 minutes to 30 minutes.

The core layers may be chemically treated in a solution, such as asolution containing one or more isocyanates, to form the desired“positive hardness gradient.” The cores are typically exposed to thesolution containing the isocyanate by immersing them in a bath at aparticular temperature for a given time. Exposure time should be greaterthan 1 minute, preferably from 1 minute to 120 minutes, more preferably5 minutes to 90 minutes, and most preferably 10 minutes to 60 minutes.In one preferred embodiment, the cores are immersed in the treatingsolution from 15 minutes to 45 minutes, more preferably from 20 minutesto 40 minutes, and most preferably from 25 minutes to 30 minutes. Bothirradiative and chemical methods promote molecular bonding, orcross-links, within the TP polymer. Radiative methods permitcross-linking and grafting in situ on finished products andcross-linking occurs at lower temperatures with radiation than withchemical processing. Chemical methods depend on the particular polymer,the presence of modifying agents, and variables in processing, such asthe level of irradiation. Significant property benefits in thethermoplastic materials can be attained and include, but are not limitedto, improved thermomechanical properties; lower permeability andimproved chemical resistance; reduced stress cracking; and overallimprovement in physical toughness.

Additional embodiments involve the use of plasticizers to treat the corelayers, thereby creating a softer outer portion of the core for a“negative” hardness gradient. The plasticizer may be reactive (such ashigher alkyl acrylates) or non-reactive (that is, phthalates,dioctylphthalate, or stearamides, etc). Other suitable plasticizersinclude, but are not limited to, oxa acids, fatty amines, fatty amides,fatty acid esters, phthalates, adipates, and sebacates. Oxa acids arepreferred plasticizers, more preferably those having at least one or twoacid functional groups and a variety of different chain lengths.Preferred oxa acids include 3,6-dioxaheptanoic acid,3,6,9-trioxadecanoic acid, diglycolic acid, 3,6,9-trioxaundecanoic acid,polyglycol diacid, and 3,6-dioxaoctanedioic acid, such as thosecommercially available from Archimica of Wilmington, Del. Any means ofchemical degradation will also result in a “negative” hardness gradient.Chemical modifications such as esterification or saponification are alsosuitable for modification of the thermoplastic core layer surface andcan result in the desired “positive hardness gradient.

Core Structure

As discussed above, the core of the golf ball of this inventionpreferably has a dual-layered structure comprising an inner core andouter core layer. Referring to FIG. 3, one version of a golf ball thatcan be made in accordance with this invention is generally indicated at(20). The ball (20) contains a dual-layered core (22) having an innercore (center) (22 a) and outer core layer (22 b) surrounded by asingle-layered cover (24). The inner core (22 a) is relatively small involume and generally has a diameter within a range of about 0.10 toabout 1.10 inches. More particularly, the inner core (22 a) preferablyhas a diameter size with a lower limit of about 0.15 or 0.25 or 0.35 or0.45 or 0.55 inches and an upper limit of about 0.60 or 0.70 or 0.80 or0.90 inches. In one preferred version, the diameter of the inner core(22 a) is in the range of about 0.025 to about 0.080 inches, morepreferably about 0.030 to about 0.075 inches. Meanwhile, the outer corelayer (22 b) generally has a thickness within a range of about 0.010 toabout 0.250 inches and preferably has a lower limit of 0.010 or 0.020 or0.025 or 0.030 inches and an upper limit of 0.070 or 0.080 or 0.100 or0.200 inches. In one preferred version, the outer core layer has athickness in the range of about 0.040 to about 0.170 inches, morepreferably about 0.060 to about 0.150 inches.

Referring to FIG. 4, in another version, the golf ball (25) contains adual-core (26) having an inner core (center) (26 a) and outer core layer(26 b). The dual-core (26) is surrounded by a multi-layered cover (28)having an inner cover layer (28 a) and outer cover layer (28 b).

The hardness of the core sub-assembly (inner core and outer core layer)is an important property. In general, cores with relatively highhardness values have higher compression and tend to have good durabilityand resiliency. However, some high compression balls are stiff and thismay have a detrimental effect on shot control and placement. Thus, theoptimum balance of hardness in the core sub-assembly needs to beattained.

In one preferred golf ball, the inner core (center) has a “positive”hardness gradient (that is, the outer surface of the inner core isharder than its geometric center); and the outer core layer has a“positive” hardness gradient (that is, the outer surface of the outercore layer is harder than the inner surface of the outer core layer.) Insuch cases where both the inner core and outer core layer each has a“positive” hardness gradient, the outer surface hardness of the outercore layer is preferably greater than the hardness of the geometriccenter of the inner core. In one preferred version, the positivehardness gradient of the inner core is in the range of about 2 to about40 Shore C units and even more preferably about 10 to about 25 Shore Cunits; while the positive hardness gradient of the outer core is in therange of about 2 to about 20 Shore C and even more preferably about 3 toabout 10 Shore C.

In an alternative version, the inner core may have a positive hardnessgradient; and the outer core layer may have a “zero” hardness gradient(that is, the hardness values of the outer surface of the outer corelayer and the inner surface of the outer core layer are substantiallythe same) or a “negative” hardness gradient (that is, the outer surfaceof the outer core layer is softer than the inner surface of the outercore layer.) For example, in one version, the inner core has a positivehardness gradient; and the outer core layer has a negative hardnessgradient in the range of about 2 to about 25 Shore C. In a secondalternative version, the inner core may have a zero or negative hardnessgradient; and the outer core layer may have a positive hardnessgradient. Still yet, in another embodiment, both the inner core andouter core layers have zero or negative hardness gradients.

In general, hardness gradients are further described in Bulpett et al.,U.S. Pat. Nos. 7,537,529 and 7,410,429, the disclosures of which arehereby incorporated by reference. Methods for measuring the hardness ofthe inner core and outer core layers along with other layers in the golfball and determining the hardness gradients of the various layers aredescribed in further detail below. The core layers have positive,negative, or zero hardness gradients defined by hardness measurementsmade at the outer surface of the inner core (or outer surface of theouter core layer) and radially inward towards the center of the innercore (or inner surface of the outer core layer). These measurements aremade typically at 2-mm increments as described in the test methodsbelow. In general, the hardness gradient is determined by subtractingthe hardness value at the innermost portion of the component beingmeasured (for example, the center of the inner core or inner surface ofthe outer core layer) from the hardness value at the outer surface ofthe component being measured (for example, the outer surface of theinner core or outer surface of the outer core layer).

Positive Hardness Gradient.

For example, if the hardness value of the outer surface of the innercore is greater than the hardness value of the inner core's geometriccenter (that is, the inner core has a surface harder than its geometriccenter), the hardness gradient will be deemed “positive” (a largernumber minus a smaller number equals a positive number.) For example, ifthe outer surface of the inner core has a hardness of 67 Shore C and thegeometric center of the inner core has a hardness of 60 Shore C, thenthe inner core has a positive hardness gradient of 7. Likewise, if theouter surface of the outer core layer has a greater hardness value thanthe inner surface of the outer core layer, the given outer core layerwill be considered to have a positive hardness gradient.

Negative Hardness Gradient.

On the other hand, if the hardness value of the outer surface of theinner core is less than the hardness value of the inner core's geometriccenter (that is, the inner core has a surface softer than its geometriccenter), the hardness gradient will be deemed “negative.” For example,if the outer surface of the inner core has a hardness of 68 Shore C andthe geometric center of the inner core has a hardness of 70 Shore C,then the inner core has a negative hardness gradient of 2. Likewise, ifthe outer surface of the outer core layer has a lesser hardness valuethan the inner surface of the outer core layer, the given outer corelayer will be considered to have a negative hardness gradient.

Zero Hardness Gradient.

In another example, if the hardness value of the outer surface of theinner core is substantially the same as the hardness value of the innercore's geometric center (that is, the surface of the inner core hasabout the same hardness as the geometric center), the hardness gradientwill be deemed “zero.” For example, if the outer surface of the innercore and the geometric center of the inner core each has a hardness of65 Shore C, then the inner core has a zero hardness gradient. Likewise,if the outer surface of the outer core layer has a hardness valueapproximately the same as the inner surface of the outer core layer, theouter core layer will be considered to have a zero hardness gradient.

More particularly, the term, “positive hardness gradient” as used hereinmeans a hardness gradient of positive 3 Shore C or greater, preferably 7Shore C or greater, more preferably 10 Shore C, and even more preferably20 Shore C or greater. The term, “zero hardness gradient” as used hereinmeans a hardness gradient of less than 3 Shore C, preferably less than 1Shore C and may have a value of zero or negative 1 to negative 10 ShoreC. The term, “negative hardness gradient” as used herein means ahardness value of less than zero, for example, negative 3, negative 5,negative 7, negative 10, negative 15, or negative 20 or negative 25. Theterms, “zero hardness gradient” and “negative hardness gradient” may beused herein interchangeably to refer to hardness gradients of negative 1to negative 10.

The inner core preferably has a geometric center hardness(H_(inner core center)) Of about 5 Shore D or greater. For example, the(H_(inner core center)) may be in the range of about 5 to about 88 ShoreD and more particularly within a range having a lower limit of about 5or 10 or 18 or 20 or 26 or 30 or 34 or 36 or 38 or 42 or 48 or 50 or 52Shore D and an upper limit of about 54 or 56 or 58 or 60 or 62 or 64 or68 or 70 or 74 or 76 or 80 or 82 or 84 or 88 Shore D. In anotherexample, the center hardness of the inner core (H_(inner core center)),as measured in Shore C units, is preferably about 10 Shore C or greater;for example, the H_(inner core center) may have a lower limit of about10 or 14 or 16 or 20 or 23 or 24 or 28 or 31 or 34 or 37 or 40 or 44Shore C and an upper limit of about 46 or 48 or 50 or 51 or 53 or 55 or58 or 61 or 62 or 65 or 68 or 71 or 74 or 76 or 78 or 79 or 80 or 84 or90 Shore C. Concerning the outer surface hardness of the inner core(H_(inner core surface)), this hardness is preferably about 12 Shore Dor greater; for example, the H_(inner core surface) may fall within arange having a lower limit of about 12 or 15 or 18 or 20 or 22 or 26 or30 or 34 or 36 or 38 or 42 or 48 or 50 or 52 Shore D and an upper limitof about 54 or 56 or 58 or 60 or 62 or 70 or 72 or 75 or 78 or 80 or 82or 84 or 86 or 90 Shore D. In one version, the outer surface hardness ofthe inner core (H_(inner core surface)), as measured in Shore C units,has a lower limit of about 13 or 15 or 18 or 20 or 22 or 24 or 27 or 28or 30 or 32 or 34 or 38 or 44 or 47 or 48 Shore C and an upper limit ofabout 50 or 54 or 56 or 61 or 65 or 66 or 68 or 70 or 73 or 76 or 78 or80 or 84 or 86 or 88 or 90 or 92 Shore C. In another version, thegeometric center hardness (H_(inner core center)) is in the range ofabout 10 Shore C to about 50 Shore C; and the outer surface hardness ofthe inner core (H_(inner core surface)) is in the range of about 5 ShoreC to about 50 Shore C.

On the other hand, the outer core layer preferably has an outer surfacehardness (H_(outer surface of OC)) of about 40 Shore D or greater, andmore preferably within a range having a lower limit of about 40 or 42 or44 or 46 or 48 or 50 or 52 and an upper limit of about 54 or 56 or 58 or60 or 62 or 64 or 70 or 74 or 78 or 80 or 82 or 85 or 87 or 88 or 90Shore D. The outer surface hardness of the outer core layer(H_(outer surface of OC)), as measured in Shore C units, preferably hasa lower limit of about 40 or 42 or 45 or 48 or 50 or 54 or 58 or 60 or63 or 65 or 67 or 720 or 72 or 73 or 76 Shore C, and an upper limit ofabout 78 or 80 or 84 or 87 or 88 or 89 or 90 or 92 or 95 Shore C. And,the inner surface of the outer core layer (H_(inner surface of OC))preferably has a hardness of about 40 Shore D or greater, and morepreferably within a range having a lower limit of about 40 or 42 or 44or 46 or 48 or 50 or 52 and an upper limit of about 54 or 56 or 58 or 60or 62 or 64 or 70 or 74 or 78 or 80 or 82 or 85 or 87 or 88 or 90 ShoreD. The inner surface hardness of the outer core layer(H_(inner surface of OC)), as measured in Shore C units, preferably hasa lower limit of about 40 or 42 or 44 or 45 or 47 or 50 or 52 or 54 or55 or 58 or 60 or 63 or 65 or 67 or 70 or 73 or 76 Shore C, and an upperlimit of about 78 or 80 or 85 or 88 or 89 or 90 or 92 or 95 Shore C.

In one embodiment, the outer surface hardness of the outer core layer(H_(outer surface of OC)), is less than the outer surface hardness(H_(inner core surface)) of the inner core by at least 3 Shore C unitsand more preferably by at least 5 Shore C.

In a second embodiment, the outer surface hardness of the outer corelayer (H_(outer surface of OC)), is greater than the outer surfacehardness (H_(inner core surface)) of the inner core by at least 3 ShoreC units and more preferably by at least 5 Shore C.

As discussed above, the inner core is preferably formed from a foamedthermoplastic or thermoset composition and more preferably foamedpolyurethanes. And, the outer core layer is formed preferably from anon-foamed thermoset composition such as polybutadiene rubber.

The core structure also has a hardness gradient across the entire coreassembly. In one embodiment, the (H_(inner core center)) is in the rangeof about 10 Shore C to about 60 Shore C, preferably about 13 Shore C toabout 55 Shore C; and the (H_(outer surface of OC)) is in the range ofabout 65 to about 96 Shore C, preferably about 68 Shore C to about 94Shore C or about 75 Shore C to about 93 Shore C, to provide a positivehardness gradient across the core assembly. The gradient across the coreassembly will vary based on several factors including, but not limitedto, the dimensions of the inner core, intermediate core, and outer corelayers.

The inner core preferably has a diameter in the range of about 0.100 toabout 1.100 inches. For example, the inner core may have a diameterwithin a range of about 0.100 to about 0.500 inches. In another example,the inner core may have a diameter within a range of about 0.300 toabout 0.800 inches. More particularly, the inner core may have adiameter size with a lower limit of about 0.10 or 0.12 or 0.15 or 0.25or 0.30 or 0.35 or 0.45 or 0.55 inches and an upper limit of about 0.60or 0.65 or 0.70 or 0.80 or 0.90 or 1.00 or 1.10 inches. As far as theouter core layer is concerned, it preferably has a thickness in therange of about 0.100 to about 0.750 inches. For example, the lower limitof thickness may be about 0.050 or 0.100 or 0.150 or 0.200 or 0.250 or0.300 or 0.340 or 0.400 and the upper limit may be about 0.500 or 0.550or 0.600 or 0.650 or 0.700 or 0.750 inches.

Dual-layered core structures containing layers with various thicknessand volume levels may be made in accordance with this invention. Forexample, in one version, the total diameter of the core structure is0.20 inches and the total volume of the core structure is 0.23 cc. Moreparticularly, in this example, the diameter of the inner core is 0.10inches and the volume of the inner core is 0.10 cc; while the thicknessof the outer core is 0.100 inches and the volume of the outer core is0.13 cc. In another version, the total core diameter is about 1.55inches and the total core volume is 31.96 cc. In this version, the outercore layer has a thickness of 0.400 inches and volume of 28.34 cc.Meanwhile, the inner core has a diameter of 0.75 inches and volume of3.62 cm. In one embodiment, the volume of the outer core layer isgreater than the volume of the inner core. In another embodiment, thevolume of the outer core layer and inner core are equivalent. In stillanother embodiment, the volume of the outer core layer is less than thevolume of the inner core. Other examples of core structures containinglayers of varying thicknesses and volumes are described below in TableA.

TABLE A Sample Core Dimensions Thermoset Foamed Total Core Total CoreOuter Core Outer Core Inner Core Volume of Example Diameter VolumeThickness Volume Diameter Inner Core A 0.30″  0.23 cc 0.100″  0.13 cc0.10″ 0.10 cc B 1.60″ 33.15 cc 0.750″ 33.05 cc 0.10″ 0.10 cc C 1.55″31.96 cc 0.225″ 11.42 cc 1.10″ 11.42 cc  D 1.55″ 31.96 cc 0.400″ 28.34cc 0.75″ 3.62 cc E 1.55″ 31.96 cc 0.525″ 28.34 cc 0.50″ 3.62 cc

In one preferred embodiment, the inner core has a specific gravity inthe range of about 0.25 to about 1.25 g/cc. Also, as discussed above,the specific gravity of the inner core may vary at different points ofthe inner core structure. That is, there may be a specific gravitygradient in the inner core. For example, in one preferred version, thegeometric center of the inner core has a density in the range of about0.25 to about 0.75 g/cc; while the outer skin of the inner core has adensity in the range of about 0.75 to about 1.50 g/cc.

Meanwhile, the outer core layer preferably has a relatively highspecific gravity. Thus, the specific gravity of the inner core layer(SG_(inner)) is preferably less than the specific gravity of the outercore layer (SG_(outer)). By the term, “specific gravity of the outercore layer” (“SG_(outer)”), it is generally meant the specific gravityof the outer core layer as measured at any point of the outer corelayer. The specific gravity values at different points in the outer corelayer may vary. That is, there may be specific gravity gradients in theouter core layer similar to the inner core. For example, the outer corelayer may have a specific gravity within a range having a lower limit ofabout 0.50 or 0.60 or 0.70 or 0.75 or 0.85 or 0.95 or 1.00 or 1.10 or1.25 or 1.30 or 1.36 or 1.40 or 1.42 or 1.48 or 1.50 or 1.60 or 1.66 or1.75 or 2.00 and an upper limit of 2.50 or 2.60 or 2.80 or 2.90 or 3.00or 3.10 or 3.25 or 3.50 or 3.60 or 3.80 or 4.00, 4.25 or 5.00 or 5.10 or5.20 or 5.30 or 5.40 or 6.00 or 6.20 or 6.25 or 6.30 or 6.40 or 6.50 or7.00 or 7.10 or 7.25 or 7.50 or 7.60 or 7.65 or 7.80 or 8.00 or 8.20 or8.50 or 9.00 or 9.75 or 10.00 g/cc.

In general, the specific gravities of the respective pieces of an objectaffect the Moment of Inertia (MOI) of the object. The Moment of Inertiaof a ball (or other object) about a given axis generally refers to howdifficult it is to change the ball's angular motion about that axis. Ifthe ball's mass is concentrated towards the center (the center piece(for example, inner core) has a higher specific gravity than the outerpiece (for example, outer core layers), less force is required to changeits rotational rate, and the ball has a relatively low Moment ofInertia. In such balls, most of the mass is located close to the ball'saxis of rotation and less force is needed to generate spin. Thus, theball has a generally high spin rate as the ball leaves the club's faceafter making impact. Conversely, if the ball's mass is concentratedtowards the outer surface (the outer piece (for example, outer corelayers) has a higher specific gravity than the center piece (forexample, inner core), more force is required to change its rotationalrate, and the ball has a relatively high Moment of Inertia. That is, insuch balls, most of the mass is located away from the ball's axis ofrotation and more force is needed to generate spin. Such balls have agenerally low spin rate as the ball leaves the club's face after makingimpact.

More particularly, as described in Sullivan, U.S. Pat. No. 6,494,795 andLadd et al., U.S. Pat. No. 7,651,415, the formula for the Moment ofInertia for a sphere through any diameter is given in the CRC StandardMathematical Tables, 24th Edition, 1976 at 20 (hereinafter CRCreference). The term, “specific gravity” as used herein, has itsordinary and customary meaning, that is, the ratio of the density of asubstance to the density of water at 4° C., and the density of water atthis temperature is 1 g/cm³.

In one embodiment, the golf balls of this invention are relatively lowspin and long distance. That is, the foam core construction, asdescribed above, wherein the inner core is made of a foamed compositionhelps provide a relatively low spin ball having good resiliency. Theinner foam cores of this invention preferably have a Coefficient ofRestitution (COR) of about 0.300 or greater; more preferably about 0.400or greater, and even more preferably about 0.450 or greater. Theresulting balls containing the dual-layered core constructions of thisinvention and cover of at least one layer preferably have a COR of about0.700 or greater, more preferably about 0.730 or greater; and even morepreferably about 0.750 to 0.810 or greater. The inner foam corespreferably have a Soft Center Deflection Index (“SCDI”) compression, asdescribed in the Test Methods below, in the range of about 50 to about190, and more preferably in the range of about 60 to about 170.

The USGA has established a maximum weight of 45.93 g (1.62 ounces) forgolf balls. For play outside of USGA rules, the golf balls can beheavier. In one preferred embodiment, the weight of the multi-layeredcore is in the range of about 28 to about 38 grams. Also, golf ballsmade in accordance with this invention can be of any size, although theUSGA requires that golf balls used in competition have a diameter of atleast 1.68 inches. For play outside of United States Golf Association(USGA) rules, the golf balls can be of a smaller size. Normally, golfballs are manufactured in accordance with USGA requirements and have adiameter in the range of about 1.68 to about 1.80 inches. As discussedfurther below, the golf ball contains a cover which may be multi-layeredand in addition may contain intermediate (casing) layers, and thethickness levels of these layers also must be considered. Thus, ingeneral, the dual-layer core structure normally has an overall diameterwithin a range having a lower limit of about 1.00 or 1.20 or 1.30 or1.40 inches and an upper limit of about 1.58 or 1.60 or 1.62 or 1.66inches, and more preferably in the range of about 1.3 to 1.65 inches. Inone embodiment, the diameter of the core sub-assembly is in the range ofabout 1.45 to about 1.62 inches.

Cover Structure

The golf ball sub-assemblies of this invention may be enclosed with oneor more cover layers. The golf ball sub-assembly may comprise themulti-layered core structure as discussed above. In other versions, thegolf ball sub-assembly includes the core structure and one or morecasing (mantle) layers disposed about the core. In one particularlypreferred version, the golf ball includes a multi-layered covercomprising inner and outer cover layers. The inner cover layer ispreferably formed from a composition comprising an ionomer or a blend oftwo or more ionomers that helps impart hardness to the ball. In aparticular embodiment, the inner cover layer is formed from acomposition comprising a high acid ionomer. A particularly suitable highacid ionomer is Surlyn 8150® (DuPont). Surlyn 8150® is a copolymer ofethylene and methacrylic acid, having an acid content of 19 wt %, whichis 45% neutralized with sodium. In another particular embodiment, theinner cover layer is formed from a composition comprising a high acidionomer and a maleic anhydride-grafted non-ionomeric polymer. Aparticularly suitable maleic anhydride-grafted polymer is Fusabond 525D®(DuPont). Fusabond 525D® is a maleic anhydride-grafted,metallocene-catalyzed ethylene-butene copolymer having about 0.9 wt %maleic anhydride grafted onto the copolymer. A particularly preferredblend of high acid ionomer and maleic anhydride-grafted polymer is an 84wt %/16 wt % blend of Surlyn 8150® and Fusabond 525D®. Blends of highacid ionomers with maleic anhydride-grafted polymers are furtherdisclosed, for example, in U.S. Pat. Nos. 6,992,135 and 6,677,401, theentire disclosures of which are hereby incorporated herein by reference.

The inner cover layer also may be formed from a composition comprising a50/45/5 blend of Surlyn® 8940/Surlyn® 9650/Nucrel® 960, and, in aparticularly preferred embodiment, the composition has a materialhardness of from 80 to 85 Shore C. In yet another version, the innercover layer is formed from a composition comprising a 50/25/25 blend ofSurlyn® 8940/Surlyn® 9650/Surlyn® 9910, preferably having a materialhardness of about 90 Shore C. The inner cover layer also may be formedfrom a composition comprising a 50/50 blend of Surlyn® 8940/Surlyn®9650, preferably having a material hardness of about 86 Shore C. Acomposition comprising a 50/50 blend of Surlyn® 8940 and Surlyn® 7940also may be used. Surlyn® 8940 is an E/MAA copolymer in which the MAAacid groups have been partially neutralized with sodium ions. Surlyn®9650 and Surlyn® 9910 are two different grades of E/MAA copolymer inwhich the MAA acid groups have been partially neutralized with zincions. Nucrel® 960 is an E/MAA copolymer resin nominally made with 15 wt% methacrylic acid.

A wide variety of materials may be used for forming the outer coverincluding, for example, polyurethanes; polyureas; copolymers, blends andhybrids of polyurethane and polyurea; olefin-based copolymer ionomerresins (for example, Surlyn® ionomer resins and DuPont HPF® 1000 andHPF® 2000, commercially available from DuPont; Iotek® ionomers,commercially available from ExxonMobil Chemical Company; Amplify® 10ionomers of ethylene acrylic acid copolymers, commercially availablefrom The Dow Chemical Company; and Clarix® ionomer resins, commerciallyavailable from A. Schulman Inc.); polyethylene, including, for example,low density polyethylene, linear low density polyethylene, and highdensity polyethylene; polypropylene; rubber-toughened olefin polymers;acid copolymers, for example, poly(meth)acrylic acid, which do notbecome part of an ionomeric copolymer; plastomers; flexomers;styrene/butadiene/styrene block copolymers;styrene/ethylene-butylene/styrene block copolymers; dynamicallyvulcanized elastomers; copolymers of ethylene and vinyl acetates;copolymers of ethylene and methyl acrylates; polyvinyl chloride resins;polyamides, poly(amide-ester) elastomers, and graft copolymers ofionomer and polyamide including, for example, Pebax® thermoplasticpolyether block amides, commercially available from Arkema Inc;cross-linked trans-polyisoprene and blends thereof; polyester-basedthermoplastic elastomers, such as Hytrel®, commercially available fromDuPont or RiteFlex®, commercially available from Ticona EngineeringPolymers; polyurethane-based thermoplastic elastomers, such asElastollan®, commercially available from BASF; synthetic or naturalvulcanized rubber; and combinations thereof. Castable polyurethanes,polyureas, and hybrids of polyurethanes-polyureas are particularlydesirable because these materials can be used to make a golf ball havinghigh resiliency and a soft feel. By the term, “hybrids of polyurethaneand polyurea,” it is meant to include copolymers and blends thereof.

Polyurethanes, polyureas, and blends, copolymers, and hybrids ofpolyurethane/polyurea are also particularly suitable for forming coverlayers. When used as cover layer materials, polyurethanes and polyureascan be thermoset or thermoplastic. Thermoset materials can be formedinto golf ball layers by conventional casting or reaction injectionmolding techniques. Thermoplastic materials can be formed into golf balllayers by conventional compression or injection molding techniques.

The compositions used to make the casing (mantle) and cover layers maycontain a wide variety of fillers and additives to impart specificproperties to the ball. For example, relatively heavy-weight andlight-weight metal fillers such as, particulate; powders; flakes; andfibers of copper, steel, brass, tungsten, titanium, aluminum, magnesium,molybdenum, cobalt, nickel, iron, lead, tin, zinc, barium, bismuth,bronze, silver, gold, and platinum, and alloys and combinations thereofmay be used to adjust the specific gravity of the ball. Other additivesand fillers include, but are not limited to, optical brighteners,coloring agents, fluorescent agents, whitening agents, UV absorbers,light stabilizers, surfactants, processing aids, antioxidants,stabilizers, softening agents, fragrance components, plasticizers,impact modifiers, titanium dioxide, clay, mica, talc, glass flakes,milled glass, and mixtures thereof.

The inner cover layer preferably has a material hardness within a rangehaving a lower limit of 70 or 75 or 80 or 82 Shore C and an upper limitof 85 or 86 or 90 or 92 Shore C. The thickness of the intermediate layeris preferably within a range having a lower limit of 0.010 or 0.015 or0.020 or 0.030 inches and an upper limit of 0.035 or 0.045 or 0.080 or0.120 inches. The outer cover layer preferably has a material hardnessof 85 Shore C or less. The thickness of the outer cover layer ispreferably within a range having a lower limit of 0.010 or 0.015 or0.025 inches and an upper limit of 0.035 or 0.040 or 0.055 or 0.080inches. Methods for measuring hardness of the layers in the golf ballare described in further detail below.

A single cover or, preferably, an inner cover layer is formed around theouter core layer. When an inner cover layer is present, an outer coverlayer is formed over the inner cover layer. Most preferably, the innercover is formed from an ionomeric material and the outer cover layer isformed from a polyurethane material, and the outer cover layer has ahardness that is less than that of the inner cover layer. Preferably,the inner cover has a hardness of greater than about 60 Shore D and theouter cover layer has a hardness of less than about 60 Shore D. In analternative embodiment, the inner cover layer is comprised of apartially or fully neutralized ionomer, a thermoplastic polyesterelastomer such as Hytrel™, commercially available form DuPont, athermoplastic polyether block amide, such as Pebax™, commerciallyavailable from Arkema, Inc., or a thermoplastic or thermosettingpolyurethane or polyurea, and the outer cover layer is comprised of anionomeric material. In this alternative embodiment, the inner coverlayer has a hardness of less than about 60 Shore D and the outer coverlayer has a hardness of greater than about 55 Shore D and the innercover layer hardness is less than the outer cover layer hardness.

As discussed above, the core structure of this invention may be enclosedwith one or more cover layers. In one embodiment, a multi-layered covercomprising inner and outer cover layers is formed, where the inner coverlayer has a thickness of about 0.01 inches to about 0.06 inches, morepreferably about 0.015 inches to about 0.040 inches, and most preferablyabout 0.02 inches to about 0.035 inches. In this version, the innercover layer is formed from a partially- or fully-neutralized ionomerhaving a Shore D hardness of greater than about 55, more preferablygreater than about 60, and most preferably greater than about 65. Theouter cover layer, in this embodiment, preferably has a thickness ofabout 0.015 inches to about 0.055 inches, more preferably about 0.02inches to about 0.04 inches, and most preferably about 0.025 inches toabout 0.035 inches, with a hardness of about Shore D 80 or less, morepreferably 70 or less, and most preferably about 60 or less. The innercover layer is harder than the outer cover layer in this version. Apreferred outer cover layer is a castable or reaction injection moldedpolyurethane, polyurea or copolymer, blend, or hybrid thereof having aShore D hardness of about 40 to about 50. In another multi-layer cover,dual-core embodiment, the outer cover and inner cover layer materialsand thickness are the same but, the hardness range is reversed, that is,the outer cover layer is harder than the inner cover layer. For thisharder outer cover/softer inner cover embodiment, the ionomer resinsdescribed above would preferably be used as outer cover material.

Manufacturing of Golf Balls

As described above, the inner core preferably is formed by a castingmethod. The outer core layer, which surrounds the inner core, is formedby molding compositions over the inner core. Compression or injectionmolding techniques may be used to form the other layers of the coresub-assembly. Then, the casing and/or cover layers are applied over thecore sub-assembly. Prior to this step, the core structure may besurface-treated to increase the adhesion between its outer surface andthe next layer that will be applied over the core. Suchsurface-treatment may include mechanically or chemically-abrading theouter surface of the core. For example, the core may be subjected tocorona-discharge, plasma-treatment, silane-dipping, or other treatmentmethods known to those in the art.

The cover layers are formed over the core or ball sub-assembly (the corestructure and any casing layers disposed about the core) using asuitable technique such as, for example, compression-molding,flip-molding, injection-molding, retractable pin injection-molding,reaction injection-molding (RIM), liquid injection-molding, casting,spraying, powder-coating, vacuum-forming, flow-coating, dipping,spin-coating, and the like. Preferably, each cover layer is separatelyformed over the ball subassembly. For example, an ethylene acidcopolymer ionomer composition may be injection-molded to producehalf-shells. Alternatively, the ionomer composition can be placed into acompression mold and molded under sufficient pressure, temperature, andtime to produce the hemispherical shells. The smooth-surfacedhemispherical shells are then placed around the core sub-assembly in acompression mold. Under sufficient heating and pressure, the shells fusetogether to form an inner cover layer that surrounds the sub-assembly.In another method, the ionomer composition is injection-molded directlyonto the core sub-assembly using retractable pin injection molding. Anouter cover layer comprising a polyurethane or polyurea composition overthe ball sub-assembly may be formed by using a casting process.

After the golf balls have been removed from the mold, they may besubjected to finishing steps such as flash-trimming, surface-treatment,marking, coating, and the like using techniques known in the art. Forexample, in traditional white-colored golf balls, the white-pigmentedcover may be surface-treated using a suitable method such as, forexample, corona, plasma, or ultraviolet (UV) light-treatment. Then,indicia such as trademarks, symbols, logos, letters, and the like may beprinted on the ball's cover using pad-printing, ink-jet printing,dye-sublimation, or other suitable printing methods. Clear surfacecoatings (for example, primer and top-coats), which may contain afluorescent whitening agent, are applied to the cover. The resultinggolf ball has a glossy and durable surface finish.

In another finishing process, the golf balls are painted with one ormore paint coatings. For example, white primer paint may be appliedfirst to the surface of the ball and then a white top-coat of paint maybe applied over the primer. Of course, the golf ball may be painted withother colors, for example, red, blue, orange, and yellow. As notedabove, markings such as trademarks and logos may be applied to thepainted cover of the golf ball. Finally, a clear surface coating may beapplied to the cover to provide a shiny appearance and protect any logosand other markings printed on the ball.

Different ball constructions can be made using the core construction ofthis invention as shown in FIGS. 3 and 4. Such golf ball constructionsinclude, for example, five-piece, and six-piece constructions. It shouldbe understood that the golf balls shown in FIGS. 3 and 4 are forillustrative purposes only, and they are not meant to be restrictive.Other golf ball constructions can be made in accordance with thisinvention.

Cores Having Three Layers

For example, multi-layered cores having an inner core, intermediate corelayer, and outer core layer, wherein the intermediate core layer isdisposed between the intermediate and outer core layers may be preparedin accordance with this invention. More particularly, as discussedabove, the inner core may be constructed from a foamed composition,preferably foamed polyurethane. Meanwhile, the intermediate and outercore layers may be formed from non-foamed thermoset or thermoplasticmaterials. Suitable thermoset and thermoplastic compositions that may beused to form the intermediate/outer core layers are discussed above. Forexample, each of the intermediate and outer core layers may be formedfrom a thermoset rubber composition. Thus, the intermediate core layermay be formed from a first thermoset rubber composition; and the outercore layer may be formed from a second thermoset rubber composition. Inanother embodiment, the intermediate core layer is formed from anon-foamed thermoset composition; and the outer core layer is formedfrom a non-foamed thermoplastic composition. In a third embodiment, theintermediate core layer is formed from a non-foamed thermoplasticcomposition; and the outer core layer is formed from a non-foamedthermoset composition. Finally, in a fourth embodiment, the intermediatecore layer is formed from a first non-foamed thermoplastic composition;and the outer core layer is formed from a second non-foamedthermoplastic compositions.

The above-discussed thermoset and thermoplastic compositions may be usedto form the intermediate and outer core layers. In one embodiment, thespecific gravity of the inner core (foamed composition) is less than thespecific gravity of the intermediate and outer core layers. The specificgravities of the intermediate and outer core layers may be the same ordifferent. In one version, the specific gravity of the intermediate corelayer is greater than the specific gravity of the outer core layer. Inanother version, the specific gravity of the outer core is greater thanthe specific gravity of the intermediate core layer.

Cores Having Two or More Foam Layers

In another example, cores having two or more layers comprising foamedcompositions may be made in accordance with this invention. In oneembodiment, a dual-core structure having an inner core layer comprisinga first foamed polyurethane composition, and an outer core layercomprising a second foamed polyurethane composition is made. The innercore layer preferably has a diameter in the range of about 0.100 toabout 1.100 inches and the outer core layer preferably has a thicknessin the range of about 0.100 to about 0.750 inches. The specific gravityof the outer core (SG_(outer)) is preferably greater than the specificgravity of the inner core (SG_(inner)). Alternatively, the inner coremay have a greater specific gravity than the outer core's specificgravity. In yet another version, the specific gravities of the inner andouter core layers are substantially equivalent. Furthermore, the innercover layer, which surrounds the core sub-assembly, may be foamed ornon-foamed. Suitable thermoset and thermoplastic compositions that maybe used to form the foam compositions for constructing the differentcore layers are discussed above.

Where more than one foam layer is used in a single golf ball, therespective foamed chemical compositions may be the same or different,and the compositions may have the same or different hardness or specificgravity levels. For example, a golf ball may contain a dual-core havinga foamed polyurethane center with a specific gravity of about 0.40 g/ccand a geometric center hardness of about 50 Shore C and a center surfacehardness of about 75 Shore C. Meanwhile, the outer core layer may bemade from a foamed highly-neutralized ionomer (HNP) composition, whereinthe outer core layer has a specific gravity of about 0.80 g/cc and asurface hardness of about 80 Shore C.

In another example, a golf ball having a foamed center made of a foamedpolyurethane composition and a surrounding outer core layer made of afoamed highly-neutralized ionomer (HNP) may be made. In one embodiment,the foamed center has a specific gravity of about 0.40 g/cc, and thefoamed outer core layer has a specific gravity of about 0.80 g/cc. In athird example, a polyurethane foam center (0.50 inch diameter) isencased in a HNP foam outer core layer (0.06 inch thickness). The innerfoamed polyurethane core has a specific gravity of 0.5 g/cc and asurface hardness of 80 Shore C, while the outer foamed HNP core has aspecific gravity of 0.90 g/cc and a surface hardness of 70 Shore C. Thedual-core is enclosed in a dual-cover, wherein the inner cover is madeof a relatively hard ionomer composition (for example, a 50/50 blend ofSurlyn® 7940 and Surlyn® 8940 or a 50/50 blend of Surlyn® 9910/Surlyn®8940) preferably having a thickness of 0.06 inches and an outer covermade of a relatively soft polyurethane composition preferably having athickness of 0.03 inches.

In a fourth example, a rigid foam outer core layer comprising athermoset polyurethane foam composition is molded over an inner core(center) comprising a HNP foam composition to provide a “hard over soft”dual-core that reduces ball spin and increases ball distance. In thisexample, the HNP foam center has a diameter of about 0.50 to about 0.80inches, and the outer core layer of cast, thermoset foam has an outerdiameter of about 1.30 to about 1.58 inches. The dual-core is enclosedin a dual-cover, wherein the inner cover is made of a relatively hardionomer composition (for example, a 50/50 blend of Surlyn® 7940 andSurlyn® 8940 or a 50/50 blend of Surlyn® 9910/Surlyn® 8940) preferablyhaving a thickness of 0.06 inches and an outer cover made of arelatively soft polyurethane composition preferably having a thicknessof 0.03 inches. In this embodiment, either the inner cover comprisingthe ionomer blend or the outer cover comprising the polyurethanepreferably contains a sufficient amount of heavy filler to adjust theweight of the golf ball so that it is at least 44 grams, preferably 45.0to 45.9 grams. In an alternative embodiment, a relatively softpolyurethane foam composition is used to form the inner core (center) asopposed to the foamed HNP composition. The soft polyurethane foammaterial used to form the inner core preferably has a different chemicalcomposition than the soft polyurethane material used to form the outercover.

Furthermore, multi-layered cores having an inner core, intermediate corelayer, and outer core layer (as discussed above) may be made, wherein atleast two of the layers comprise foamed compositions. The core may haveadjoining foam layers, for example, the inner core and intermediate corelayers may be made of foamed polyurethane compositions, while the outercore layer may be made of a non-foamed thermoset or thermoplasticcomposition. For example, a polybutadiene foamed center (0.50 inchdiameter) is encased in a partially-neutralized ionomer foamedintermediate core layer (0.050 inch thickness). The inner foamedpolybutadiene core may have a specific gravity of 0.85 g/cc and asurface hardness of 65 Shore C, while the partially-neutralized ionomerfoamed intermediate core layer may have a specific gravity of 0.70 g/ccand a surface hardness of 85 Shore C. An outer core layer made of arelative hard HNP ionomer composition having a specific gravity of 0.70g/cc and a surface hardness of 85 Shore C surrounds the intermediatecore layer. The three-layered core structure (“triple core”) is enclosedin a dual-cover, wherein the inner cover is made of a relatively hardionomer composition and an outer cover made of a relatively softpolyurethane composition.

In an alternative version, the core may have a non-foamed thermoset orthermoplastic layer disposed between two foam layers. For example, theinner and outer core layers may be made of a foamed polyurethanecomposition, and these layers may form a sandwich around an intermediatecore layer made of a non-foamed thermoset or thermoplastic compositionsuch as polybutadiene rubber.

In the above core sub-assembly constructions, any of the foamed ornon-foamed compositions may further comprises nanoclay particulate,preferably in an amount of about 0.1 to about 9.0% by weight based onweight of composition.

Test Methods

Hardness.

The center hardness of a core is obtained according to the followingprocedure. The core is gently pressed into a hemispherical holder havingan internal diameter approximately slightly smaller than the diameter ofthe core, such that the core is held in place in the hemisphericalportion of the holder while concurrently leaving the geometric centralplane of the core exposed. The core is secured in the holder byfriction, such that it will not move during the cutting and grindingsteps, but the friction is not so excessive that distortion of thenatural shape of the core would result. The core is secured such thatthe parting line of the core is roughly parallel to the top of theholder. The diameter of the core is measured 90 degrees to thisorientation prior to securing. A measurement is also made from thebottom of the holder to the top of the core to provide a reference pointfor future calculations. A rough cut is made slightly above the exposedgeometric center of the core using a band saw or other appropriatecutting tool, making sure that the core does not move in the holderduring this step. The remainder of the core, still in the holder, issecured to the base plate of a surface grinding machine. The exposed‘rough’ surface is ground to a smooth, flat surface, revealing thegeometric center of the core, which can be verified by measuring theheight from the bottom of the holder to the exposed surface of the core,making sure that exactly half of the original height of the core, asmeasured above, has been removed to within 0.004 inches. Leaving thecore in the holder, the center of the core is found with a center squareand carefully marked and the hardness is measured at the center markaccording to ASTM D-2240. Additional hardness measurements at anydistance from the center of the core can then be made by drawing a lineradially outward from the center mark, and measuring the hardness at anygiven distance along the line, typically in 2 mm increments from thecenter. The hardness at a particular distance from the center should bemeasured along at least two, preferably four, radial arms located 180°apart, or 90° apart, respectively, and then averaged. All hardnessmeasurements performed on a plane passing through the geometric centerare performed while the core is still in the holder and without havingdisturbed its orientation, such that the test surface is constantlyparallel to the bottom of the holder, and thus also parallel to theproperly aligned foot of the durometer.

The outer surface hardness of a golf ball layer is measured on theactual outer surface of the layer and is obtained from the average of anumber of measurements taken from opposing hemispheres, taking care toavoid making measurements on the parting line of the core or on surfacedefects, such as holes or protrusions. Hardness measurements are madepursuant to ASTM D-2240 “Indentation Hardness of Rubber and Plastic byMeans of a Durometer.” Because of the curved surface, care must be takento ensure that the golf ball or golf ball sub-assembly is centered underthe durometer indenter before a surface hardness reading is obtained. Acalibrated, digital durometer, capable of reading to 0.1 hardness unitsis used for the hardness measurements. The digital durometer must beattached to, and its foot made parallel to, the base of an automaticstand. The weight on the durometer and attack rate conforms to ASTMD-2240.

In certain embodiments, a point or plurality of points measured alongthe “positive” or “negative” gradients may be above or below a line fitthrough the gradient and its outermost and innermost hardness values. Inan alternative preferred embodiment, the hardest point along aparticular steep “positive” or “negative” gradient may be higher thanthe value at the innermost portion of the inner core (the geometriccenter) or outer core layer (the inner surface)—as long as the outermostpoint (i.e., the outer surface of the inner core) is greater than (for“positive”) or lower than (for “negative”) the innermost point (i.e.,the geometric center of the inner core or the inner surface of the outercore layer), such that the “positive” and “negative” gradients remainintact.

As discussed above, the direction of the hardness gradient of a golfball layer is defined by the difference in hardness measurements takenat the outer and inner surfaces of a particular layer. The centerhardness of an inner core and hardness of the outer surface of an innercore in a single-core ball or outer core layer are readily determinedaccording to the test procedures provided above. The outer surface ofthe inner core layer (or other optional intermediate core layers) in adual-core ball are also readily determined according to the proceduresgiven herein for measuring the outer surface hardness of a golf balllayer, if the measurement is made prior to surrounding the layer with anadditional core layer. Once an additional core layer surrounds a layerof interest, the hardness of the inner and outer surfaces of any inneror intermediate layers can be difficult to determine. Therefore, forpurposes of the present invention, when the hardness of the inner orouter surface of a core layer is needed after the inner layer has beensurrounded with another core layer, the test procedure described abovefor measuring a point located 1 mm from an interface is used.

Also, it should be understood that there is a fundamental differencebetween “material hardness” and “hardness as measured directly on a golfball.” For purposes of the present invention, material hardness ismeasured according to ASTM D2240 and generally involves measuring thehardness of a flat “slab” or “button” formed of the material. Surfacehardness as measured directly on a golf ball (or other sphericalsurface) typically results in a different hardness value. The differencein “surface hardness” and “material hardness” values is due to severalfactors including, but not limited to, ball construction (that is, coretype, number of cores and/or cover layers, and the like); ball (orsphere) diameter; and the material composition of adjacent layers. Italso should be understood that the two measurement techniques are notlinearly related and, therefore, one hardness value cannot easily becorrelated to the other. Shore hardness (for example, Shore C or Shore Dhardness) was measured according to the test method ASTM D-2240.

Compression.

As disclosed in Jeff Dalton's Compression by Any Other Name, Science andGolf IV, Proceedings of the World Scientific Congress of Golf (EricThain ed., Routledge, 2002) (“J. Dalton”), several different methods canbe used to measure compression, including Atti compression, Riehlecompression, load/deflection measurements at a variety of fixed loadsand offsets, and effective modulus. For purposes of the presentinvention, compression refers to Soft Center Deflection Index (“SCDI”).The SCDI is a program change for the Dynamic Compression Machine (“DCM”)that allows determination of the pounds required to deflect a core 10%of its diameter. The DCM is an apparatus that applies a load to a coreor ball and measures the number of inches the core or ball is deflectedat measured loads. A crude load/deflection curve is generated that isfit to the Atti compression scale that results in a number beinggenerated that represents an Atti compression. The DCM does this via aload cell attached to the bottom of a hydraulic cylinder that istriggered pneumatically at a fixed rate (typically about 1.0 ft/s)towards a stationary core. Attached to the cylinder is an LVDT thatmeasures the distance the cylinder travels during the testing timeframe.A software-based logarithmic algorithm ensures that measurements are nottaken until at least five successive increases in load are detectedduring the initial phase of the test. The SCDI is a slight variation ofthis set up. The hardware is the same, but the software and output haschanged. With the SCDI, the interest is in the pounds of force requiredto deflect a core x amount of inches. That amount of deflection is 10%percent of the core diameter. The DCM is triggered, the cylinderdeflects the core by 10% of its diameter, and the DCM reports back thepounds of force required (as measured from the attached load cell) todeflect the core by that amount. The value displayed is a single numberin units of pounds.

Drop Rebound.

By “drop rebound,” it is meant the number of inches a sphere willrebound when dropped from a height of 72 inches in this case, measuringfrom the bottom of the sphere. A scale, in inches is mounted directlybehind the path of the dropped sphere and the sphere is dropped onto aheavy, hard base such as a slab of marble or granite (typically about 1ft wide by 1 ft high by 1 ft deep). The test is carried out at about72-75° F. and about 50% RH

Coefficient of Restitution (“COR”).

The COR is determined according to a known procedure, wherein a golfball or golf ball sub-assembly (for example, a golf ball core) is firedfrom an air cannon at two given velocities and a velocity of 125 ft/s isused for the calculations. Ballistic light screens are located betweenthe air cannon and steel plate at a fixed distance to measure ballvelocity. As the ball travels toward the steel plate, it activates eachlight screen and the ball's time period at each light screen ismeasured. This provides an incoming transit time period which isinversely proportional to the ball's incoming velocity. The ball makesimpact with the steel plate and rebounds so it passes again through thelight screens. As the rebounding ball activates each light screen, theball's time period at each screen is measured. This provides an outgoingtransit time period which is inversely proportional to the ball'soutgoing velocity. The COR is then calculated as the ratio of the ball'soutgoing transit time period to the ball's incoming transit time period(COR=V_(out)/V_(in)=T_(in)/T_(out)).

Density.

The density refers to the weight per unit volume (typically, g/cm³) ofthe material and can be measured per ASTM D-1622.

EXAMPLES

The present invention is illustrated further by the following Examples,but these Examples should not be construed as limiting the scope of theinvention.

In the following Examples, different foam formulations were used toprepare core samples using the above-described molding methods. Thedifferent formulations are described in Tables 1-5 below. Theconcentrations of ingredients in the formulations are in weight percent,based on total weight of the composition, unless otherwise indicated.The resulting spherical cores were measured for density and tested forcompression and Coefficient of Restitution (COR) using the test methodsas described above and the results are reported in Tables 1-5 below.

TABLE 1 Spherical Foam Core Samples Example No. 1 2 3 4 5 6 6.5% MDIPrepolymer 41 43.72 45.01 33.58 49.48 31.83 Mondur MR 7.33 13.64 MondurCD 19.75 Mondur ML 17 13.06 8.06 Poly THF 650 22.2 13.06 29.01 CAPA 303113.77 13.77 4 CAPA 3091 27.86 CAPA 4101 CAPA 4801 D.I. Water 0.5 0.500.45 0.50 0.45 0.50 Niax 1500 0.75 0.75 0.75 0.75 0.75 Varox MPBCIrganox 1135 Dabco 33LV 0.2 0.2 0.2 0.2 0.2 Garamite 1958 0.375 0.3750.375 0.375 0.375 0.375 Total Parts 76.345 76.315 76.315 76.325 75.0576.305 Density 0.54 0.7 0.6 0.53 0.6 Compression 35 106 −217 −242 −217CoR @125 ft/s 0.434 0.503 0.52 0.278 0.41 6.5% MDI Prepolymer is madefrom 4,4′-MDI and polytetramethylene glycol ether Mondur ™ MR -polymeric MDI, available from Bayer. Mondur ™ CD - modified 4,4′-MDI,available from Bayer. Mondur ™ ML - isomer mixture of 2,4 and 4,4′- MDI,available from Bayer. Poly THF ™ 650 - 650 molecular weightpolyetratmethylene ether glycol (PTMEG), available from BASF. CAPA ™3031 - low molecular weight trifunctional polycaprolactone polyol,available from Perstorp CAPA ™ 3091 - polyester triol terminated byprimary hydroxyl groups, available from Perstorp. CAPA ™ 4101 -tetra-functional polyol terminated with primary hydroxyl groups,available from Perstorp. CAPA ™ 4801 - tetra-functional polyolterminated with primary hydroxyl groups, available from Perstorp. Niax ™L-1500 - silicone surfactant from Momentive Specialty Chemicals, Inc.Vanox ™ MBPC - antioxidant, available from R. T. Vanderbuilt. Irganox ™1135 - antioxidant, available BASF. Dabco ™ 33LV - tertiary aminecatalyst, available from Air Products. Garamite ™ 1958 - mixed mineralthixotropes (clay mixture), available from Southern Clay Products, Inc..

TABLE 2 Spherical Foam Core Samples Example No. 7 8 9 10 11 12 6.5% MDIPrepolymer 21.67 45.81 49.22 45.01 45.01 55.8 Mondur MR 18.46 7.46 8.017.33 7.33 9.08 Mondur CD Mondur ML Poly THF 650 34.33 20.57 13 22.2 22.2CAPA 3031 0.7 4 9.66 CAPA 3091 CAPA 4101 CAPA 4801 D.I. Water 0.53 0.450.45 0.45 0.45 0.45 Niax 1500 0.75 0.75 0.75 0.75 0.75 0.75 Varox MPBC0.375 Irganox 1135 0.38 Dabco 33LV 0.2 0.2 0.2 0.2 0.2 0.2 Garamite 19580.375 0.375 0.375 0.375 0.375 0.375 Total Parts 76.315 76.315 76.00576.69 76.695 76.315 Density 0.46 0.4 Compression −245 −109 CoR @125 ft/s0.388 0.515

TABLE 3 Spherical Foam Core Samples Example No. 13 14 15 16 17 18 6.5%MDI Prepolymer 68.81 44.28 33.1 42.39 49.48 40.75 Mondur MR 12.49 17.0511.96 8.06 11.5 Mondur CD Mondur ML Poly THF 650 CAPA 3031 5.79 5.0472.86 2.37 2 CAPA 3091 CAPA 4101 12.67 21.48 17.79 15 22.27 CAPA 4801D.I. Water 0.39 0.45 0.67 0.48 0.45 0.48 Niax 1500 0.75 0.75 0.75 0.750.75 0.75 Varox MPBC Irganox 1135 Dabco 33LV 0.2 0.2 0.2 0.2 0.2 0.2Garamite 1958 0.375 0.375 0.38 0.38 0.38 0.38 Total Parts 76.315 76.26276.49 76.32 76.32 76.33 Density 0.52 0.35 0.64 0.39 0.46 0.39Compression −200 −144 45 −135 −165 −120 CoR @125 ft/s 0.54 0.534 0.5710.553 0.537 0.543

TABLE 4 Spherical Foam Core Samples Example No. 19 20 21 22 6.5% MDI47.83 56.05 29.18 19.58 Prepolymer Mondur MR 7.78 9.12 12.51 16.68Mondur CD Mondur ML Poly THF 650 CAPA 3031 CAPA 3091 CAPA 4101 18.9218.11 17.37 20.23 CAPA 4801 16.1 15.44 17.98 D.I. Water 0.45 0.61 0.50.52 Niax 1500 0.75 0.75 0.75 0.75 Varox MPBC Irganox 1135 Dabco 33LV0.2 0.2 0.2 0.2 Garamite 1958 0.38 0.38 0.38 0.38 Total Parts 76.31101.32 76.33 76.32 Density 0.42 0.66 0.51 Compression −165 −169 −100 CoR@125 ft/s 0.609 0.492 0.425

TABLE 5 Spherical Foam Core Samples Example No. 23 24 25 26 6.5% MDI43.87 50.63 37.21 43.57 Prepolymer Mondur MR 9.63 5.63 13.07 9.56 MondurCD Mondur ML Poly THF 650 CAPA 3031 CAPA 3091 CAPA 4101 18.36 15.9821.18 16.15 CAPA 4801 D.I. Water 0.47 0.45 0.49 0.47 Niax 1500 0.75 0.750.75 0.75 Varox MPBC Irganox 1135 Dabco 33LV 0.2 0.2 0.2 0.2 Garamite1958 0.38 0.38 0.38 0.38 Total Parts 76.31 76.33 76.34 76.33 Density0.46 0.57 0.43 0.48 Compression −164 −169 −137 −147 CoR @125 ft/s 0.5780.600 0.541 0.571

In the following Examples (Samples A to D), different formulations wereused to prepare dual-core samples having a foam center and surroundingthermoset outer core layer using the above-described molding methods.The sample cores were tested for compression (DCM), Coefficient ofRestitution (COR), and hardness using the above-described test methodsand the results are reported below in Table 10. In the formulations, theconcentrations are in parts per hundred (phr) unless otherwiseindicated. As used herein, the term “parts per hundred,” also known as“phr,” is defined as the number of parts by weight of a particularcomponent present in a mixture, relative to 100 parts by weight of thebase rubber component. Mathematically, this can be expressed as theweight of an ingredient divided by the total weight of the polymer,multiplied by a factor of 100.

Sample A (0.5″ Foamed Center)

In this Sample, the foam formulation in below Table 6 was used toprepare an inner core having a diameter of 0.5 inches.

TABLE 6 (Foam Center of Sample A) Ingredient Parts 6.5% MDI Prepolymer45.010 Mondur ™ 582 (2.5 fn) 7.330 Poly THF ™ 650 22.200 Deionized Water0.450 Niax ™ L-1500 surfactant 0.750 Dabco ™ 33LV 0.200 Garamite ™ 19580.375

The following rubber formulation (Table 7) was molded about the foamedinner core and cured to form a thermoset rubber outer core layer.

TABLE 7 (Rubber Outer Core Layer of Sample A) Ingredient Parts *Buna ™CB23 100.0 Zinc Diacrylate (ZDA) 35.0 **Perkadox BC 0.5 ZincPentachlorothiophenol (ZnPCTP) 0.5 Zinc Oxide 14.9 *Buna ™ CB23 -polybutadiene rubber, available from Lanxess Corp. **Perkadox ™ BC,peroxide free-radical initiator, available from Akzo Nobel.

The dual-layered core of Sample A (foam center and thermoset rubberouter core layer with a center diameter of 0.5) inches was tested forhardness and the core was found to have a hardness gradient (across theentire core as measured at points in millimeters (mm) from the geometriccenter) in the range of about 21 Shore C to about 89 Shore C. Thehardness of the core measured at the geometric center was about 21 ShoreC and the hardness of the core measured at about 20 mm from thegeometric center (that is, the surface of the outer core layer) wasabout 89 Shore C. The hardness values measured at various points alongthis core structure are described in Table 14 below and the hardnessplot is shown in FIG. 5.

Sample B (0.5″ Foamed Center)

In this Sample B, the foam formulation in below Table 8 was used toprepare an inner core having a diameter of 0.5 inches.

TABLE 8 (Foam Center of Sample B) Ingredient Parts 6.5% MDI Prepolymer55.800 Mondur ™ 582 (2.5 fn) 9.080 CAPA ™ 3031 9.660 Deionized Water0.450 Niax ™ L-1500 surfactant 0.750 Dabco ™ 33LV 0.200 Garamite ™ 19580.375

The same rubber formulation as described above in Sample A (Table 7) wasmolded about the foam center of Sample B and cured to form a thermosetrubber outer core layer.

Sample C (0.5″ Foamed Center)

In this Sample C, the foam formulation in below Table 9 was used toprepare an inner core having a diameter of 0.5 inches.

TABLE 9 (Foam Center of Sample C) Ingredient Parts 6.5% MDI Prepolymer44.280 Mondur ™ 582 (2.5 fn) 12.490 CAPA ™ 3031 5.047 Deionized Water0.450 Niax ™ L-1500 surfactant 0.750 Dabco ™ 33LV 0.200 Garamite ™ 19580.375

The same rubber formulation as described above in Sample A (Table 7) wasmolded about the foam center of Sample C and cured to form a thermosetrubber outer core layer.

TABLE 10 Properties of Core Samples (A-C) Center Compression COR@125 ft/Surface Hard- Hardness Sample (DCM) sec Hardness ness Gradient A 850.816 88.9 22.1 66.8 B 81 0.797 86.1 46.0 40.2 C 81 0.806 87.0 43.7 43.3

Sample D (0.75″ Foamed Center)

In this Sample, the foam formulation in below Table 11 was used toprepare an inner core having a diameter of 0.75 inches.

TABLE 11 (Foam Center of Sample D) Ingredient Parts 6.5% MDI Prepolymer47.830 Mondur ™ 582 (2.5 fn) 7.780 CAPA ™ 4101 18.920 Deionized Water0.450 Niax ™ L-1500 surfactant 0.750 Dabco ™ 33LV 0.200 Garamite ™19580.380

In this Sample D, the following rubber formulation (Table 12) was moldedabout the foamed inner core and cured to form a thermoset rubber outercore layer. Different core samples having different densities (SamplesD1-D5) were prepared and are further described in Table 12 below.

TABLE 12 (Rubber Outer Core Layer of Sample D) Ingredient Parts Buna ™CB23 100.0 Zinc Diacrylate (ZDA) 36.0 Perkadox BC 0.5 ZincPentachlorothiophenol (ZnPCTP) 0.5 Zinc Oxide 21.3

The Sample D1-D5 cores were tested for compression (DCM), Coefficient ofRestitution (COR), and Hardness using the above-described test methodsand the results are reported below in Table 13.

TABLE 13 Properties of Core Samples (D1-D5) Density of Surface CenterHardness Foamed Center Compression COR@125 Hardness Hardness GradientSample (g/cm³) (DCM) ft/sec (Shore C) (Shore C) (Shore C) D-1 0.40 800.779 86.6 33.5 53.0 D-2 0.46 78 0.775 86.4 31.8 54.3 D-3 0.59 77 0.77086.4 34. 52.3 D-4 0.75 78 0.769 87.3 43.0 44.3 D-5 0.83 75 0.766 87.437.4 50.0

The dual-layered core of Sample D-2 (foam center and thermoset rubberouter core layer having a center diameter of 0.75 inches) was tested forhardness and the core was found to have a hardness gradient (across theentire core as measured at points in millimeters (mm) from the geometriccenter) in the range of about 32 Shore C to about 86 Shore C. Thehardness of the core measured at the geometric center was about 32 ShoreC and the hardness of the core measured at about 20 mm from thegeometric center (that is, the surface of the outer core layer) wasabout 86 Shore C. The hardness values measured at various points alongthe core structure are described in Table 14 below and the hardness plotis shown in FIG. 5.

TABLE 14 Hardness Properties of Core Samples (C and D-2) Distance fromGeometric Center of Core Sample Hardness Gradient of Hardness Gradientof (mm) Sample C (Shore C) Sample D-2 (Shore C)  0 (Center) 21 31.8  220.8 32.6  4 25 35.7  6 28.1 35.1  8 72 37.8 10 72.8 70.9 12 73.1 70.214 72.7 70.2 16 76.5 76.9 18 82.6 81.8 20 (Surface) 88.9 86.4

In the following Examples, different foam formulations were used toprepare core samples using the above-described molding methods. Thedifferent formulations are described in Tables 15 and 16 below.

TABLE 15 (Sample E) (Comparative) Ingredient Weight Percent 4,4Methylene Diphenyl Diisocyanate (MDI) 17.26% *Mondur ™ 582 (2.5 fn)polymeric methylene 9.70% diphenyl diisocyanate (p-MDI)Polyetratmethylene ether glycol (PTMEG 42.26% 2000) Poly THF ™ 650molecular weight 29.09% polyetratmethylene ether glycol (PTMEG) Water0.45% **Niax ™ L-1500 silicone-based surfactant 0.98% Garamite ™ 1958mixed clay particulate 0.00% Dabco ™ 33LV tertiary amine catalys 0.26%

As shown in above Table 15, a polyurethane foam composition that did notcontain any clay particulate, was used to prepare a spherical core(Sample E). The resulting core had relatively poor foam cell size anduniformity as shown in the photograph of FIG. 6. Some of the foam cellsappeared to be relatively large and it is believed that gas would tendto diffuse out of some of the cells in this sample.

TABLE 16 (Sample F) Ingredient Weight Percent 4,4 Methylene DiphenylDiisocyanate (MDI) 17.06% *Mondur ™ 582 (2.5 fn) polymeric methylene9.54% diphenyl diisocyanate (p-MDI) Polyetratmethylene ether glycol(PTMEG 42.21% 2000) Poly THF ™ 650 molecular weight 29.00%polyetratmethylene ether glycol (PTMEG) Water 0.45% **Niax ™ L-1500silicone-based surfactant 0.99% Garamite ™ 1958 nanoclay 0.49% Dabco ™33LV tertiary amine catalys 0.26%

As shown in above Table 16, a polyurethane foam composition, thatcontained nanoclay particulate, was used to prepare a spherical core(Sample F). The resulting core had relatively good foam cell size anduniformity as shown in the photograph of FIG. 7. Some of the foam cellsin this sample appeared to be relatively small in size.

As discussed above, manufacturing the polyurethane foam generallyinvolves two reactions: i) a “blowing” reaction, wherein an isocyanategroup reacts with water to yield a thermally unstable carbamic acid thatdecomposes to give an amine, carbon dioxide, and heat; and ii) a“polymerization” reaction, wherein the isocyanate groups react with apolyol to generate urethane linkages.

In general, both reactions occur when the reactants are combined andmixed together. Thus, it is important that the relative rates ofreaction be balanced. The respective reaction rates should be controlledin order to produce a stable foam structure having good physicalproperties. If the blowing reaction takes place too fast relative to thepolymerization reaction, the mixture will not have sufficient viscosityto build-up the internal polyurethane foam struts and the foam cellswill coalesce and collapse on themselves. On the other hand, if thepolymerization reaction occurs too quickly, it may lead to problems withcell growth, cell opening, and cell geometry. It is believed that addingthe clay filler to the polyurethane or other composition in accordancewith this invention helps regulate the relative rates of reaction sothat foam cells will be generated and stabilized. The foam will riseuniformly and the internal struts, which connect the foam cells, willhave enough strength to uphold the foam. When the foam stops rising, itwill cure to form a hardened material having a foamed matrix. In FIG. 8,the polyurethane foam composition containing clay filler(above-described Sample F) is shown in a vertical position. The foam hasrisen completely and uniformly and has sufficient strength to maintainits stand-up position. In comparison, the foam composition that does notcontain clay filler (above-described Sample E) also is shown. In SampleF, the foam has not risen to a sufficient height. The foam does not havesufficient strength and has collapsed on itself.

It is understood that the golf ball compositions, constructions, andproducts described and illustrated herein represent only someembodiments of the invention. It is appreciated by those skilled in theart that various changes and additions can be made to compositions,constructions, and products without departing from the spirit and scopeof this invention. It is intended that all such embodiments be coveredby the appended claims.

We claim:
 1. A golf ball, comprising: i) an inner core layer comprisinga foamed composition, the inner core layer having a diameter in therange of about 0.100 to about 1.100 inches and a specific gravity(SG_(inner)), the foamed composition comprising mineral fillerparticulate in an amount of about 0.1 to about 9.0% by weight; ii) anintermediate core layer comprising a foamed composition, theintermediate core layer being disposed about the inner core layer andhaving a specific gravity (SG_(intermediate)), wherein the SG_(inner) isgreater than the SG_(intermediate); and iii) an outer core layer anon-foamed thermoset or thermoplastic comprising composition, the outercore layer being disposed about the intermediate core layer.
 2. The golfball of claim 1, wherein the inner core comprises a foamed polybutadienecomposition and has a SG_(inner) of 0.85; the intermediate core layercomprises a foamed partially-neutralized ethylene acid copolymer ionomercomposition and has a SG_(intermediate) of 0.70; and the outer corelayer comprises a non-foamed highly-neutralized ethylene acid copolymerionomer composition and has an SG_(outer) of 0.70.
 3. The golf ball ofclaim 2, wherein the inner core has a surface hardness of 65 Shore C;the intermediate core layer has a surface hardness of 85 Shore C; andthe outer core layer has a surface hardness of 85 Shore C.
 4. The golfball of claim 1, wherein the mineral filler particulate has a particlesize in the range of about 1 to about 25 microns.
 5. The golf ball ofclaim 1, wherein the mineral filler particulate comprises clayparticulate.
 6. The golf ball of claim 5, wherein the clay particulatecomprises a mixture of different clay particles, the particles having anaverage specific gravity in the range of about 1.30 to about 3.00 g/cc.7. The golf ball of claim 5, wherein the clay particulate is nanoclayparticulate.
 8. The golf ball of claim 5, wherein the clay particulatehas a chemically-modified surface, the surface being chemically-modifiedwith a compound selected from the group consisting of ammoniumcompounds, protonated amines, organic phosphonium ions, and/oraminocarboxylic acids.
 9. A golf ball, comprising: i) an inner corelayer comprising a foamed composition, the inner core layer having adiameter in the range of about 0.100 to about 1.100 inches and aspecific gravity (SGinner), the foamed composition comprising mineralfiller particulate in an amount of about 0.1 to about 9.0% by weight;ii) an intermediate core layer comprising a non-foamed thermoset orthermoplastic composition, the intermediate core layer being disposedabout the inner core layer and having a thickness in the range of about0.100 to about 0.750 inches and a specific gravity (SGintermediate),wherein the SGinner is greater than the SGintermediate; and iii) anouter core layer comprising a foamed composition, the outer core layerbeing disposed about the intermediate core layer.
 10. The golf ball ofclaim 9, wherein the inner core comprises a foamed polyurethanecomposition; the intermediate core layer comprises a non-foamedpolybutadiene rubber composition; and the outer core layer comprises afoamed polyurethane composition.
 11. The golf ball of claim 9, whereinthe mineral filler particulate comprises clay particulate.
 12. The golfball of claim 11, wherein the clay particulate comprises a mixture ofdifferent clay particles, the particles having an average specificgravity in the range of about 1.30 to about 3.00 g/cc.
 13. The golf ballof claim 11, wherein the clay particulate is nanoclay particulate. 14.The golf ball of claim 11, wherein the clay particulate has achemically-modified surface, the surface being chemically-modified witha compound selected from the group consisting of ammonium compounds,protonated amines, organic phosphonium ions, and/or aminocarboxylicacids.
 15. A golf ball, comprising: i) an inner core layer comprising afoamed composition, the inner core layer having a diameter in the rangeof about 0.100 to about 1.100 inches and a specific gravity(SG_(inner)), the foamed composition comprising mineral fillerparticulate in an amount of about 0.1 to about 9.0% by weight; ii) anintermediate core layer comprising a foamed composition, theintermediate core layer being disposed about the inner core layer andhaving a thickness in the range of about 0.050 to about 0.400 inches anda specific gravity (SG_(intermediate)), wherein the SG_(intermediate) isgreater than the SG_(inner); and iii) an outer core layer comprising anon-foamed thermoset or thermoplastic composition, the outer core layerbeing disposed about the intermediate core layer and having a thicknessin the range of about 0.200 to about 0.750 inches and a specific gravity(SG_(outer)), wherein the SG_(outer) is greater than the SG_(inner). 16.The golf ball of claim 15, wherein the mineral filler particulatecomprises clay particulate.
 17. The golf ball of claim 16, wherein theclay particulate comprises a mixture of different clay particles, theparticles having an average specific gravity in the range of about 1.30to about 3.00 g/cc.
 18. The golf ball of claim 16, wherein the clayparticulate is nanoclay particulate.
 19. The golf ball of claim 16,wherein the clay particulate has a chemically-modified surface, thesurface being chemically-modified with a compound selected from thegroup consisting of ammonium compounds, protonated amines, organicphosphonium ions, and/or aminocarboxylic acids.